CA2231539C - Coating composition containing polyester polymers with terminal carbamate groups and polymeric polyol derived from ethylenically unsaturated monomers - Google Patents
Coating composition containing polyester polymers with terminal carbamate groups and polymeric polyol derived from ethylenically unsaturated monomers Download PDFInfo
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- CA2231539C CA2231539C CA002231539A CA2231539A CA2231539C CA 2231539 C CA2231539 C CA 2231539C CA 002231539 A CA002231539 A CA 002231539A CA 2231539 A CA2231539 A CA 2231539A CA 2231539 C CA2231539 C CA 2231539C
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
Abstract
An adherent film-forming composition comprising a carbamate-functional polyester polymer or oligomer, a hydroxy functional polymer derived from ethylenically unsaturated monomers and an aminoplast cross-linking agent is disclosed. The coating composition can be used to produce clear coats in composite color plus clear coatings exhibiting good levels of acid etch resistance as well as high intercoat adhesion. Also disclosed are a method of applying a composite color plus clear coating to a substrate and the coated article prepared by such a method.
Description
CA 02231~39 1998-04-02 WO97/19139 PCT~US96/18701 COATING COMPOSITION CONTAINING POLYESTER POLYMERS
FROM ETHYLENICALLY UNSATURATED MONOMERS
Field of th~ Tnv~ntion The present invention relates to film-forming compositions containing polyester polymers with terminal carbamate groups in combination with hydroxyl functional polymers and crosslinking agents for said compositions, and to the use of such film-forming compositions as clear coats in color plus clear composite coatings.
BAckgrolln~ of the Invention Coating compositions based on acrylic polymers and aminoplast crosslinking agents are particularly desirable as aut~motive top coats because they have excellent durability, hardness, gloss and appearance. However, such coating compositions, when used as clear coats in color plus clear composite coatings, are particularly susceptible to acid etching. Acid etching is a phenomenon associated with acidic rain water, which is common in many urban and industrial areas. When acidic rain water, also known as acid rain, accumulates on a horizontal section of an automobile such as a hood or trunk deck, it spots and can actually etch away the clear coat leaving a blemish that cannot be polished out. It has been found that acrylic polymers containing pendant or terminal carbamate groups can be cured with aminoplast crosslinking agents to give acid etch resistant clear coats.
Publications that disclose such polymers are US 5,356,669, US
5,336,566, EPO 0,594,142 Al and EPO 0,590,068 Al.
CA 02231~39 1998-04-02 WO97/19139 PCT~US96/18701 A problem associated with curable coating compositions based on acrylic polymers containing pendant carbamate groups and aminoplast curing agents is that the compositions do not have particularly good intercoat adhesion. This problem presents itself when the compositions are used as clear coats in composite color plus clear composite coatings, especially during repair procedures which involve applying the clear ~ilm-forming composition to a flawed area of a previously applied color plus clear composite coating. The clear coats can actually delaminate ~rom underlying layers of ~ilm.
SummAry of th~ Invention The adhesion problems associated with ~ilm-forming compositions based on acrylic polymers contA;n;ng pendant carbamate groups and aminoplast curing agents can be alleviated by coating compositions comprising a polymer or oligomer containing repeating ester groups in the backbone and containing a plurality of terminal carbamate groups in combination with polymeric polyols and an aminoplast curing agent. The polyester polymer or oligomer and the polymeric polyols are present in amounts su~icient to impart good etch resistance and to increase intercoat adhesion, without adversely a~ecting the humidity resistance o~ the coating.
The best balance o~ etch re~istance and intercoat adhesion is achieved by using carbamate functional polyesters and acrylic polyols in combination with fully alkylated melamine.
Speci~ically, the present invention provides an adherent ~ilm-~orming composition comprising:
(a) 25 to 70 percent by weight o~ a polymer or oligomer containing repeating ester groups in the polymer or oligomer backbone and WO97/19139 PCT~S96/18701 cont~;nlng a plurality of terminal carbamate groups of the structure:
(b) 30 to 75 percent by weight of a hydroxyl functional polymer derived from ethylenically unsaturated monomers; and (c) 25 to 50 percent by weight of an aminoplast crosslinking agent;
the percentages by weight of (a) and (b) being ba6ed on total resin solids weight of (a) plus (b); the percentage by weight of ~c) being based on total weight of resin solids in the film-~orming composition. Preferably, the percentage by weight of (a) plus (b) is from 25 to 75 percent by weight and is based on the total weight of resin solids in the film-forming composition.
Also, the present invention provides a method of applying a composite color plus clear coating to a substrate in which the film-forming composition described above is the clear coat. Further, the present invention provides for coated articles prepared by the above described method.
Det~ile~ De~criptio~
The film-forming composition comprises a polymer or oligomer containing repeating ester groups in the backbone.
The polymer or oligomer typically is an oligomeric polyester and/or a polymeric polyester. The polymers or oligomers having a plurality of ester groups in the backbone are prepared by a ~n~n~ation or addition reaction in which the ester groups are repeating, i.e., CA 02231~39 1998-04-02 -- C -- O --A suitable polyester can be prepared by the 5 esterification of a polycarboxylic acid or an anhydride thereof with a polyol and/or an epoxide. The polycarboxylic acids used to prepare the polyester consist primarily of monomeric polycarboxylic acids or anhydrides thereof having 2 to 18 carbon atoms per molecule. Among the acids that are useful are phthalic acid, hexahydrophthalic acid, adipic acid, sebacic acid, maleic acid, and other dicarboxylic acids of various types. Minor amounts of monobasic acids can be included in the reaction mixture, for example, benzoic acid, stearic acid, acetic acid, and oleic acid. Also, higher ~5 carboxylic acids can be used, Eor example, trimellitic acid and tricarballylic acid. Anhydrides of the acids referred to above, where they exist, can be used in place of the acid.
Also, lower alkyl esters of the acids can be used, for example, dimethyl glutarate and dimethyl terephthalate.
Polyols that can be used to prepare the polyester include diols such as alkylene glycols. Specific examples include ethylene glycol, l,6-hexanediol, neopentyl glycol, and 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate.
Other suitable glycols include hydrogenated sisphenol A, cycloh~n~odiol, cyclohexanedimethanol, caprolactone-based diols such as the reaction product of e-caprolactone and ethylene glycol, hydroxy-alkylated bisphenols, polyether glycols such as poly(oxytetramethylene~glycol, and the like.
Although the polyol component can comprise all diols, polyols of higher ~unctionality can also be used. It is preferred that the polyol be a mixture of at least one diol;
and at least one triol, or one polyol of higher functionality.
Examples of polyols of higher functionality would include WO97/19139 PCT~US96/18701 trimethylol ethane, trimethylol propane, pentaerythritol, and the like. Triols are preferred. The mole ratio of polyols of higher functionality to diol is les6 than 3.3/l, preferably up to l.4/l.
In the preferred embodiment, a polyester is prepared from an esterdiol such as 2,2'-dimethyl-3-hydroxypropyl-2,2~-dimethyl-3-hydroxypropionate and a triol such as trimethylolpropane.
The polyester has terminal carbamate groups of the structure:
_ O NH2 The carbamate groups can be incorporated into the polyester by first forming a hydroxyalkyl carbamate that can be reacted with the polyacids and polyols used in forming the polyester. A polyester oligomer can be prepared by reacting a polycarboxylic acid such as those mentioned above with a hydroxyalkyl carbamate. An example of a hydroxyalkyl carbamate is the reaction product of ~mmnn;a and propylene carbonate. The hydroxyalkyl carbamate is condensed with acid functionality on the polyester or polycarboxylic acid, yielding terminal carbamate functionality. Terminal carbamate functional groups can also be incorporated into the polyester by reacting isocyanic acid with a hydroxy functional polyester. Also, carbamate ~unctionality can be incorporated into the polyester by reacting a hydroxy functional polyester with urea.
Carbamate groups can be incorporated into the polyester by a transcarbamalation reaction.
CA 02231~39 1998-04-02 WO97/19139 PCT~US96/18701 In this reaction, a low molecular weight carbamate ~unctional material derived ~rom a low molecular weight alcohol or glycol ether such as methyl carbamate iB reacted with the hydroxyl groups of a hydroxyl functional polyester, yielding a carbamate ~unctional polyester and the original alcohol or glycol ether. The low molecular weight carbamate ~unctional material derived ~rom an alcohol or glycol ether is first prepared by reacting the alcohol or glycol ether with urea in the pre~ence of a catalyst. Suitable alcohol~ include lower molecular weight aliphatic, cycloaliphatic, and aromatic alcohols such as methanol, ethanol, propanol, butanol, cyclnh~nnl, 2-ethylh~noll and 3-methylbutanol. Suitable glycol ethers include ethylene glycol methyl ether and propylene glycol methyl ether. Propylene glycol methyl ether is pre~erred.
Besides carbamate ~unctionality the polyester polymers and oligomers may contain other ~unctional groups such as hydroxyl, carboxylic acid and/or anhydride groups. The equivalent weight o~ the polyesters cont~in-ng terminal 20 carbamate groups will be ~rom about 140 to 2500, based on equivalents o~ carbamate groups. The equivalent weight is a calculated value based on the relative amounts of the various ingredients used in making the polyester, and is based on the solids o~ the material.
The polyesters typically have weight average molecular weights o~ about lOOO to 30,000, pre~erably lOOO to lO,OOO as determined by gel permeation chromatography using polystyrene as a st~n~rd.
The hydroxyl ~unctional polymer derived ~rom ethylenically unsaturated monomers can be represented by r~n~o~ly repeating units according to the ~ollowing ~ormula:
-WO97/19139 PCT~US96/18701 [- (CH2 - C) -]x ( )Y
Q - O - H
where R is H or CH3; Z is a repeating unit derived from one or more different polymerizable ethylenically unsaturated monomers; and x is, on a weight basis, from 30 to 70 percent, y is, on a weight ba6is, from 30 to 70 percent, with the percentage of x plus y being e~ual to lOO percent. Q
represents a divalent linking group, preferably -Q- is represented by -COO-Q'- where Q' is a divalent linking group.
Q' can be a divalent aliphatic linking group, preferably of 2 to 8 carbon atoms, e.g., C2H4,C3H6, C4H8, and the like; or a divalent cycloaliphatic linking group, preferably of up to 8 carbon atoms, e.g., cyclohexyl, and the like. However, other divalent linking groups can be used, depending on the techni~ue used to prepare the polymer.
Typically, the hydroxyl functional polymers derived from ethylenically unsaturated monomers are acrylic copolymers which are copolymers of one or more hydroxy alkyl esters of acrylic acid or methacrylic acid, and, optionally, one or more other polymerizable ethylenically unsaturated monomers.
Examples of hydroxy alkyl esters are hydroxyethyl acrylate and methacrylate and hydroxypropyl acrylate and methacrylate.
Example of other polymerizable ethylenically unsaturated monomers include alkyl esters of acrylic or methacrylic acid including methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Other polymerizable ethylenically unsaturated m~no~rs include vinyl aromatic compounds such as styrene and vinyl toluene; nitriles such as acrylonitrile and methacrylonitrile; vinyl and vinylidene halides such as vinyl chloride and vinylidene fluoride; vinyl CA 02231~39 1998-04-02 ~VO97/19139 PCTnUS96/18701 esters such as vinyl acetate; and acid functional monomers such as acrylic and methacrylic acid.
The hydroxy functional polymer can be prepared ~y solution polymerization techniques in the presence o~ suitable initiators such as organic peroxides or azo compounds, ~or example, benzoyl peroxide or N,N-azobis(isobutyronitrile).
The polymerization can be carried out in an organic solution in which the monom~rs are soluble by techniques conventional in the art. Alternatively, the hydroxy ~unctional polymer can be prepared by aqueous emulsion or dispersion polymerization techniques well known in the art.
The hydroxy functional polymer typically has an equivalent weight o~ less than 5000, pre~erably within the range of 140 to 2500, based on equivalents of reactive hydroxyl groups. The equivalent weight is a calculated value based on the relative amounts o~ the various ingredients used in making the acrylic material and is based on the solids of the hydroxyl ~unctional acrylic polymer.
In addition, the hydrox.y ~unctional polymer has a weight average molecular weight o~ ~rom about 1000 to 30,000, preferably from about 2000 to 10,000 as determined by gel permeation chromatography using polystyrene as a standard.
The aminoplast crosslinking agents useful in the present invention are obtained ~rom the reaction of ~ormaldehyde with an amine and/or an amide. Melamine, urea, or benzogn~n~in~
cnn~n~ates are preferred. However, aminoplast condensates prepared ~rom other amines or amides can be used, for example, aldehyde condensates of ylycouril, which are use~ul in formulating powder coatings. Most o~ten, formaldehyde iB used as the aldehyde; however, other aldehydes such as acetaldehyde, crotonaldehyde, and benzaldehyde are also 6uitable CA 02231~39 1998-04-02 The aminoplast crosslinking agent has a plurality of functional groups, for example, alkylated methylol groups, that are reactive with the terminal carbamate groups present in the polyester polymer or oligomer and with the hydroxyl groups associated with the polymeric polyol.
The preferred aminoplast crosslinking agent is a mel~m;n~-formaldehyde condensate that contains methylol groups that have been further etherified with an alcohol, preferably one that contains 1 to 6 carbon atoms. Any monohydric alcohol can be employed for this purpose, including methanol, ethanol, isobutanol, and cycloh~nol. Most preferably, a blend of methanol and n-butanol is used, resulting in a melamine-formaldehyde c~n~n~ate that is, on average, 75 percent methylated and 25 percent butylated.
Most preferably, the aminoplast crosslin~.ing agent is a fully alkylated aminoplast crosslinking agent. By the term "fully alkylated" is meant that the alkylol groups associated with the reaction product of an aldehyde with an amine and/or an amide have been etherified to an extent that the alkoxy groups make up at least eighty (80) percent by weight of the functional groups.
A fully alkylated aminoplast crosslinking agent results in optimum intercoat adhesion.
The film-forming composition of the present invention typically has a calculated hydroxyl value of less than 70, preferably about 15 to about 50, based on the solid weight of the film-forming composition. The calculated hydroxyl value is calculated from the relative amounts of the various ingredients used in making the film-forming composition, rather than from experimental titration measurement. Hydroxyl values greater than 70 are undesirable because they result in cured films with poor acid etch resistance.
For the polyester polymer or oligomer with terminal carbamate groups, amounts greater than 70 percent by weight are undesirable because the humidity resistance o~ the cured film su~ers; whereas amounts less than 25 percent by weight are undesirable due to poor acid etch resistance of the cured ~ilm. For the hydroxy functional polymer, amounts greater than 75 percent by weight are undesirable because the acid etch resistance of the cured ~ilm su~ers; whereas amounts less than 30 percent by weight are unde6irable because humidity resistance o~ the cured film su~fers. For the aminoplast crosslinking agent, amounts greater than 50 percent by weight are undesirable because o~ poor acid etch resistance in the cured film; whereas amounts less than 25 percent by weight are undesirable because o~ poor cured ~ilm properties.
lS Optionally, a diluent can be present in the film-forming composition that serves to reduce the viscosity o~ the coating composition. If the coating composition is solvent-borne, the diluent typically comprises an organic solvent. Examples of suitable solvents include alcohols such as ethanol, isopropanol, n-butanol, and the like; esters such as n-butyl acetate, n-hexyl acetate, pentyl propionate, and the like;
ethers such as the monoethyl, monobutyl and monohexyl ethers o~ ethylene glycol, and the like; ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and the like; aromatic hydrocarbons such as xylene, or toluene, and the like; aliphatic or alicyclic hydrocarbons such as the various petroleum naphthas and cyclohexane; and mixtures thereof The film-forming composition can also be waterborne. For example, the composition can contain an acid functional polymer that can be neutralized with amines and dissolved or dispersed in water. Also, it is possible to prepare an CA 02231~39 1998-04-02 WO97/19139 PCT~US96/18701 aqueous dispersion o~ the polymer of the film-forming composition in microparticulate form by imparting high stress using a homogenizer. This latter technique is described in U.S. Patent No. 5,071,904.
If the coating composition is waterborne, the diluent can optionally contain water-soluble organic cosolvents, for example alcohols with up to about eight carbon atoms such as methanol, ethanol, propanol, butanol, isobutanol, or mixtures thereof; or glycol ethers such as the monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and the like.
When present, diluents are typically used at a level o~
up to about 50 percent, pre~erably up to about 40 percent by weight, based on the total weight of the ~ilm-forming composition.
The film-~orming composition can also be used in particulate form, i.e., as a powder coating, in which the acrylic polymer and the oligomer or polymer cont~;n;ng the repeating ester groups are chosen such that they have a glass transition temperature (Tg) greater than 60~C. These materials can then be combined with an aldehyde c~n~n~ate o~
glycouril, as previously mentioned, to form a powder film-forming composition.
The coating composition is a thermosetting composition and typically contains catalysts to accelerate the curing reactions. Typically, the catalysts are acidic materials.
Sul~onic acids, substituted sulfonic acids and amine neutralized sulfonic acids are preferred, for example, p-toluene sul~onic acid, dodecyl benzene sulfonic acid, dinonylnaphthalene disulfonic acid, and the like. The catalyst is usually present in an amount of from 0.50 to 5.0 percent, pre~erably ~rom 0.5 to l.O percent, the percentages CA 02231~39 1998-04-02 WO97/19139 PCT~S96/18701 based on the total weight of resin solids in the coating composition.
The coating composition can contain other optional ingredients, such as co-reactive resinous materials;
plasticizers; anti-oxidants; W light absorbers; surfactants;
flow control agents; anti-settling agents; and the like. When present, these materials are generally used at a level up to 25 percent, preferably up to 10 percent by weight, the percentages based on the total weight of resin solids in the coating composition.
The film-forming composition can be applied to any of the various substrates to which it adheres. Specific examples of suitable substrates include metals, wood, glass, cloth, plastic, foam, elastomeric substrates, and the like.
Typically, the substrate is metal or plastic. Optionally, the substrate could have been previously coated with a primer coating composition, or with a pigmented basecoat and the film-forming composition of the present invention applied as a clear coat over the pigmented base coat to form a color plu~
clear composite coating.
The composition~ can be applied by conventional means including brushing, dipping, flow coating, spraying, and the like. Preferably, they are applied by spraying. The usual spray techniques and equipment ~or air-spraying or electrosta~ic spraying can be used.
When the ~ilm-forming composition is used as a clear coat in a color plu~ clear composite coating, pigmented base coat is first applied to a substrate at a uniform fllm thickness of from about 0.25 to about 1.5 mils. The base coat is then ~lashed," that is, it is left to stand at temperatures ranging from the ambient temperature to 80~C for about 10 seconds to 30 minutes, before another coating composition is CA 02231~39 1998-04-02 WO97/19139 PCT~US96/18701 applied to it. Then, typically, the clear coating composition o~ the present invention is applied over the coated substrate - in one or more coats to a uni~orm ~ilm thickness ~rom 0.5 to 5.0 mils. The substrate is then ~lashed again and ~inally S baked until the ~ilm i8 cured, typically ~or about 20 minutes to about 40 minutes at ~rom about 100~C to about 200~C to produce the coated article.
The base coating compositions are those well known in the art as described, ~or example, in U.S. Patent No. 4,681,811, column l, line 56 to column 4, line 2.
Illustrating the invention are the ~ollowing examples that are not to be considered as limiting the invention to their details. All parts and percentages in the examples as well as throughout the speci~ication are by weight unless otherwise indicated.
MPT.~ A
A hydroxyl ~unctional acrylic copolymer was prepared ~rom the ~ollowing ingredients:
Ingr~l; ~ntS Weight in parts Tn; tiAl ~h~rge xylene lO.7 SO~VESSO lool lO.7 isobutanol 4 3 ~h A rge I
hydroxypropyl acrylate 40.0 butyl methacrylate l9.0 butyl acrylate l9.0 styrene 20.0 30 acrylic acid 2.0 t-dodecyl mercaptan 0.5 1 aromatic ~olvent mixture available ~rom ~xxon Chemical Co WO97/19139 PCT~US96/18701 ~h~rge II
Tngr~;~nts Weight in parts xylene 8.7 SOLVESSO l00 6.4 S VAZO 672 5 o ~h~rge III
SOLVESSO lO0 l.l VAZO 67 0.4 ~h~rge IV
10 SOLVESSO lOO l.l VAZO 67 0.4 The initial charge was added to a 5-liter round bottom 4-neck ~lask equipped with mechanical agitation, nitrogen inlet, reflux c~n~er, and two dropping ~unnels. The charge was heated under a nitrogen ~lanket to re~lux (115~C). At re~lux, Charges I and II were simultaneously and uniformly added over a two hour period maintaining re~lux conditions. Upon completion o~ Charges I and II, Charge III was added and the reaction held ~or one hour. Charge IV was added and the reaction held one more hour. The polymer was characterized as having 69~ solids, hydroxy value o~ 95, and peak molecular weight o~ 7000 ~MPTR B
A c~rh~m~te ~unctional polyester polymer was prepared ~rom the ~ollowing ingredients:
22,2'-dimethylazobi~(isobutyronitrile) available from E~.I du l?ont de Nemourl3 & Co., Inc .
Tngre~;~nts Weight in ~arts 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3- 196.8 hydroxypropyl propionate deionized H2O lO.O
5 trimethylolpropane 42.9 ~utyl ~tannoic acid 0.6 triphenylphosphite 0.8 deionized X2O 3 0 methylhexahydrophth~lic anhydride158.3 10 deioni~ed H2O lO.O
butyl stannoic acid 0 5 triphenylphosphite 0 5 DOWANOL PM 2.0 }5DOWANOL PM r~rh~mfte (37~ solution in DOWANOL PM)4 318.9 DOWANOL PM 10.0 DOWANOL PM 105.0 The first ingredient was charged to a suitable reactor equipped with a glycol recovery column. Deionized H2O
was added to the reactor as a rinse for the first ingredient.
Trimethylolpropane, butyl stannoic acid, and triphenylphosphite were then added to the reactor, followed by a deionized H2O rinse. Methylh~hydrophthalic anhydride, with a subsequent deionized H2O rinse, was then added to the reactor followed by heating the reaction mlxture to 77~C and sparging with nitrogen for 20 minutes. The reaction mixture temperature was then raised to 210~C and H2O was removed from the reactor with the nitrogen sparge. The reaction was continued until an acid value of 10.2 was obtained and the batch was then cooled to 140 C. The intermediate resin had a hydroxyl value of 156.6. DOWANOL PM and butyl stannoic acid were added to the reactor as a slurry, followed by addition of -3 1-methoxy-2-propanol avallable ~rom DOW rh~m;rAl Co.
FROM ETHYLENICALLY UNSATURATED MONOMERS
Field of th~ Tnv~ntion The present invention relates to film-forming compositions containing polyester polymers with terminal carbamate groups in combination with hydroxyl functional polymers and crosslinking agents for said compositions, and to the use of such film-forming compositions as clear coats in color plus clear composite coatings.
BAckgrolln~ of the Invention Coating compositions based on acrylic polymers and aminoplast crosslinking agents are particularly desirable as aut~motive top coats because they have excellent durability, hardness, gloss and appearance. However, such coating compositions, when used as clear coats in color plus clear composite coatings, are particularly susceptible to acid etching. Acid etching is a phenomenon associated with acidic rain water, which is common in many urban and industrial areas. When acidic rain water, also known as acid rain, accumulates on a horizontal section of an automobile such as a hood or trunk deck, it spots and can actually etch away the clear coat leaving a blemish that cannot be polished out. It has been found that acrylic polymers containing pendant or terminal carbamate groups can be cured with aminoplast crosslinking agents to give acid etch resistant clear coats.
Publications that disclose such polymers are US 5,356,669, US
5,336,566, EPO 0,594,142 Al and EPO 0,590,068 Al.
CA 02231~39 1998-04-02 WO97/19139 PCT~US96/18701 A problem associated with curable coating compositions based on acrylic polymers containing pendant carbamate groups and aminoplast curing agents is that the compositions do not have particularly good intercoat adhesion. This problem presents itself when the compositions are used as clear coats in composite color plus clear composite coatings, especially during repair procedures which involve applying the clear ~ilm-forming composition to a flawed area of a previously applied color plus clear composite coating. The clear coats can actually delaminate ~rom underlying layers of ~ilm.
SummAry of th~ Invention The adhesion problems associated with ~ilm-forming compositions based on acrylic polymers contA;n;ng pendant carbamate groups and aminoplast curing agents can be alleviated by coating compositions comprising a polymer or oligomer containing repeating ester groups in the backbone and containing a plurality of terminal carbamate groups in combination with polymeric polyols and an aminoplast curing agent. The polyester polymer or oligomer and the polymeric polyols are present in amounts su~icient to impart good etch resistance and to increase intercoat adhesion, without adversely a~ecting the humidity resistance o~ the coating.
The best balance o~ etch re~istance and intercoat adhesion is achieved by using carbamate functional polyesters and acrylic polyols in combination with fully alkylated melamine.
Speci~ically, the present invention provides an adherent ~ilm-~orming composition comprising:
(a) 25 to 70 percent by weight o~ a polymer or oligomer containing repeating ester groups in the polymer or oligomer backbone and WO97/19139 PCT~S96/18701 cont~;nlng a plurality of terminal carbamate groups of the structure:
(b) 30 to 75 percent by weight of a hydroxyl functional polymer derived from ethylenically unsaturated monomers; and (c) 25 to 50 percent by weight of an aminoplast crosslinking agent;
the percentages by weight of (a) and (b) being ba6ed on total resin solids weight of (a) plus (b); the percentage by weight of ~c) being based on total weight of resin solids in the film-~orming composition. Preferably, the percentage by weight of (a) plus (b) is from 25 to 75 percent by weight and is based on the total weight of resin solids in the film-forming composition.
Also, the present invention provides a method of applying a composite color plus clear coating to a substrate in which the film-forming composition described above is the clear coat. Further, the present invention provides for coated articles prepared by the above described method.
Det~ile~ De~criptio~
The film-forming composition comprises a polymer or oligomer containing repeating ester groups in the backbone.
The polymer or oligomer typically is an oligomeric polyester and/or a polymeric polyester. The polymers or oligomers having a plurality of ester groups in the backbone are prepared by a ~n~n~ation or addition reaction in which the ester groups are repeating, i.e., CA 02231~39 1998-04-02 -- C -- O --A suitable polyester can be prepared by the 5 esterification of a polycarboxylic acid or an anhydride thereof with a polyol and/or an epoxide. The polycarboxylic acids used to prepare the polyester consist primarily of monomeric polycarboxylic acids or anhydrides thereof having 2 to 18 carbon atoms per molecule. Among the acids that are useful are phthalic acid, hexahydrophthalic acid, adipic acid, sebacic acid, maleic acid, and other dicarboxylic acids of various types. Minor amounts of monobasic acids can be included in the reaction mixture, for example, benzoic acid, stearic acid, acetic acid, and oleic acid. Also, higher ~5 carboxylic acids can be used, Eor example, trimellitic acid and tricarballylic acid. Anhydrides of the acids referred to above, where they exist, can be used in place of the acid.
Also, lower alkyl esters of the acids can be used, for example, dimethyl glutarate and dimethyl terephthalate.
Polyols that can be used to prepare the polyester include diols such as alkylene glycols. Specific examples include ethylene glycol, l,6-hexanediol, neopentyl glycol, and 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate.
Other suitable glycols include hydrogenated sisphenol A, cycloh~n~odiol, cyclohexanedimethanol, caprolactone-based diols such as the reaction product of e-caprolactone and ethylene glycol, hydroxy-alkylated bisphenols, polyether glycols such as poly(oxytetramethylene~glycol, and the like.
Although the polyol component can comprise all diols, polyols of higher ~unctionality can also be used. It is preferred that the polyol be a mixture of at least one diol;
and at least one triol, or one polyol of higher functionality.
Examples of polyols of higher functionality would include WO97/19139 PCT~US96/18701 trimethylol ethane, trimethylol propane, pentaerythritol, and the like. Triols are preferred. The mole ratio of polyols of higher functionality to diol is les6 than 3.3/l, preferably up to l.4/l.
In the preferred embodiment, a polyester is prepared from an esterdiol such as 2,2'-dimethyl-3-hydroxypropyl-2,2~-dimethyl-3-hydroxypropionate and a triol such as trimethylolpropane.
The polyester has terminal carbamate groups of the structure:
_ O NH2 The carbamate groups can be incorporated into the polyester by first forming a hydroxyalkyl carbamate that can be reacted with the polyacids and polyols used in forming the polyester. A polyester oligomer can be prepared by reacting a polycarboxylic acid such as those mentioned above with a hydroxyalkyl carbamate. An example of a hydroxyalkyl carbamate is the reaction product of ~mmnn;a and propylene carbonate. The hydroxyalkyl carbamate is condensed with acid functionality on the polyester or polycarboxylic acid, yielding terminal carbamate functionality. Terminal carbamate functional groups can also be incorporated into the polyester by reacting isocyanic acid with a hydroxy functional polyester. Also, carbamate ~unctionality can be incorporated into the polyester by reacting a hydroxy functional polyester with urea.
Carbamate groups can be incorporated into the polyester by a transcarbamalation reaction.
CA 02231~39 1998-04-02 WO97/19139 PCT~US96/18701 In this reaction, a low molecular weight carbamate ~unctional material derived ~rom a low molecular weight alcohol or glycol ether such as methyl carbamate iB reacted with the hydroxyl groups of a hydroxyl functional polyester, yielding a carbamate ~unctional polyester and the original alcohol or glycol ether. The low molecular weight carbamate ~unctional material derived ~rom an alcohol or glycol ether is first prepared by reacting the alcohol or glycol ether with urea in the pre~ence of a catalyst. Suitable alcohol~ include lower molecular weight aliphatic, cycloaliphatic, and aromatic alcohols such as methanol, ethanol, propanol, butanol, cyclnh~nnl, 2-ethylh~noll and 3-methylbutanol. Suitable glycol ethers include ethylene glycol methyl ether and propylene glycol methyl ether. Propylene glycol methyl ether is pre~erred.
Besides carbamate ~unctionality the polyester polymers and oligomers may contain other ~unctional groups such as hydroxyl, carboxylic acid and/or anhydride groups. The equivalent weight o~ the polyesters cont~in-ng terminal 20 carbamate groups will be ~rom about 140 to 2500, based on equivalents o~ carbamate groups. The equivalent weight is a calculated value based on the relative amounts of the various ingredients used in making the polyester, and is based on the solids o~ the material.
The polyesters typically have weight average molecular weights o~ about lOOO to 30,000, pre~erably lOOO to lO,OOO as determined by gel permeation chromatography using polystyrene as a st~n~rd.
The hydroxyl ~unctional polymer derived ~rom ethylenically unsaturated monomers can be represented by r~n~o~ly repeating units according to the ~ollowing ~ormula:
-WO97/19139 PCT~US96/18701 [- (CH2 - C) -]x ( )Y
Q - O - H
where R is H or CH3; Z is a repeating unit derived from one or more different polymerizable ethylenically unsaturated monomers; and x is, on a weight basis, from 30 to 70 percent, y is, on a weight ba6is, from 30 to 70 percent, with the percentage of x plus y being e~ual to lOO percent. Q
represents a divalent linking group, preferably -Q- is represented by -COO-Q'- where Q' is a divalent linking group.
Q' can be a divalent aliphatic linking group, preferably of 2 to 8 carbon atoms, e.g., C2H4,C3H6, C4H8, and the like; or a divalent cycloaliphatic linking group, preferably of up to 8 carbon atoms, e.g., cyclohexyl, and the like. However, other divalent linking groups can be used, depending on the techni~ue used to prepare the polymer.
Typically, the hydroxyl functional polymers derived from ethylenically unsaturated monomers are acrylic copolymers which are copolymers of one or more hydroxy alkyl esters of acrylic acid or methacrylic acid, and, optionally, one or more other polymerizable ethylenically unsaturated monomers.
Examples of hydroxy alkyl esters are hydroxyethyl acrylate and methacrylate and hydroxypropyl acrylate and methacrylate.
Example of other polymerizable ethylenically unsaturated monomers include alkyl esters of acrylic or methacrylic acid including methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Other polymerizable ethylenically unsaturated m~no~rs include vinyl aromatic compounds such as styrene and vinyl toluene; nitriles such as acrylonitrile and methacrylonitrile; vinyl and vinylidene halides such as vinyl chloride and vinylidene fluoride; vinyl CA 02231~39 1998-04-02 ~VO97/19139 PCTnUS96/18701 esters such as vinyl acetate; and acid functional monomers such as acrylic and methacrylic acid.
The hydroxy functional polymer can be prepared ~y solution polymerization techniques in the presence o~ suitable initiators such as organic peroxides or azo compounds, ~or example, benzoyl peroxide or N,N-azobis(isobutyronitrile).
The polymerization can be carried out in an organic solution in which the monom~rs are soluble by techniques conventional in the art. Alternatively, the hydroxy ~unctional polymer can be prepared by aqueous emulsion or dispersion polymerization techniques well known in the art.
The hydroxy functional polymer typically has an equivalent weight o~ less than 5000, pre~erably within the range of 140 to 2500, based on equivalents of reactive hydroxyl groups. The equivalent weight is a calculated value based on the relative amounts o~ the various ingredients used in making the acrylic material and is based on the solids of the hydroxyl ~unctional acrylic polymer.
In addition, the hydrox.y ~unctional polymer has a weight average molecular weight o~ ~rom about 1000 to 30,000, preferably from about 2000 to 10,000 as determined by gel permeation chromatography using polystyrene as a standard.
The aminoplast crosslinking agents useful in the present invention are obtained ~rom the reaction of ~ormaldehyde with an amine and/or an amide. Melamine, urea, or benzogn~n~in~
cnn~n~ates are preferred. However, aminoplast condensates prepared ~rom other amines or amides can be used, for example, aldehyde condensates of ylycouril, which are use~ul in formulating powder coatings. Most o~ten, formaldehyde iB used as the aldehyde; however, other aldehydes such as acetaldehyde, crotonaldehyde, and benzaldehyde are also 6uitable CA 02231~39 1998-04-02 The aminoplast crosslinking agent has a plurality of functional groups, for example, alkylated methylol groups, that are reactive with the terminal carbamate groups present in the polyester polymer or oligomer and with the hydroxyl groups associated with the polymeric polyol.
The preferred aminoplast crosslinking agent is a mel~m;n~-formaldehyde condensate that contains methylol groups that have been further etherified with an alcohol, preferably one that contains 1 to 6 carbon atoms. Any monohydric alcohol can be employed for this purpose, including methanol, ethanol, isobutanol, and cycloh~nol. Most preferably, a blend of methanol and n-butanol is used, resulting in a melamine-formaldehyde c~n~n~ate that is, on average, 75 percent methylated and 25 percent butylated.
Most preferably, the aminoplast crosslin~.ing agent is a fully alkylated aminoplast crosslinking agent. By the term "fully alkylated" is meant that the alkylol groups associated with the reaction product of an aldehyde with an amine and/or an amide have been etherified to an extent that the alkoxy groups make up at least eighty (80) percent by weight of the functional groups.
A fully alkylated aminoplast crosslinking agent results in optimum intercoat adhesion.
The film-forming composition of the present invention typically has a calculated hydroxyl value of less than 70, preferably about 15 to about 50, based on the solid weight of the film-forming composition. The calculated hydroxyl value is calculated from the relative amounts of the various ingredients used in making the film-forming composition, rather than from experimental titration measurement. Hydroxyl values greater than 70 are undesirable because they result in cured films with poor acid etch resistance.
For the polyester polymer or oligomer with terminal carbamate groups, amounts greater than 70 percent by weight are undesirable because the humidity resistance o~ the cured film su~ers; whereas amounts less than 25 percent by weight are undesirable due to poor acid etch resistance of the cured ~ilm. For the hydroxy functional polymer, amounts greater than 75 percent by weight are undesirable because the acid etch resistance of the cured ~ilm su~ers; whereas amounts less than 30 percent by weight are unde6irable because humidity resistance o~ the cured film su~fers. For the aminoplast crosslinking agent, amounts greater than 50 percent by weight are undesirable because o~ poor acid etch resistance in the cured film; whereas amounts less than 25 percent by weight are undesirable because o~ poor cured ~ilm properties.
lS Optionally, a diluent can be present in the film-forming composition that serves to reduce the viscosity o~ the coating composition. If the coating composition is solvent-borne, the diluent typically comprises an organic solvent. Examples of suitable solvents include alcohols such as ethanol, isopropanol, n-butanol, and the like; esters such as n-butyl acetate, n-hexyl acetate, pentyl propionate, and the like;
ethers such as the monoethyl, monobutyl and monohexyl ethers o~ ethylene glycol, and the like; ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and the like; aromatic hydrocarbons such as xylene, or toluene, and the like; aliphatic or alicyclic hydrocarbons such as the various petroleum naphthas and cyclohexane; and mixtures thereof The film-forming composition can also be waterborne. For example, the composition can contain an acid functional polymer that can be neutralized with amines and dissolved or dispersed in water. Also, it is possible to prepare an CA 02231~39 1998-04-02 WO97/19139 PCT~US96/18701 aqueous dispersion o~ the polymer of the film-forming composition in microparticulate form by imparting high stress using a homogenizer. This latter technique is described in U.S. Patent No. 5,071,904.
If the coating composition is waterborne, the diluent can optionally contain water-soluble organic cosolvents, for example alcohols with up to about eight carbon atoms such as methanol, ethanol, propanol, butanol, isobutanol, or mixtures thereof; or glycol ethers such as the monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and the like.
When present, diluents are typically used at a level o~
up to about 50 percent, pre~erably up to about 40 percent by weight, based on the total weight of the ~ilm-forming composition.
The film-~orming composition can also be used in particulate form, i.e., as a powder coating, in which the acrylic polymer and the oligomer or polymer cont~;n;ng the repeating ester groups are chosen such that they have a glass transition temperature (Tg) greater than 60~C. These materials can then be combined with an aldehyde c~n~n~ate o~
glycouril, as previously mentioned, to form a powder film-forming composition.
The coating composition is a thermosetting composition and typically contains catalysts to accelerate the curing reactions. Typically, the catalysts are acidic materials.
Sul~onic acids, substituted sulfonic acids and amine neutralized sulfonic acids are preferred, for example, p-toluene sul~onic acid, dodecyl benzene sulfonic acid, dinonylnaphthalene disulfonic acid, and the like. The catalyst is usually present in an amount of from 0.50 to 5.0 percent, pre~erably ~rom 0.5 to l.O percent, the percentages CA 02231~39 1998-04-02 WO97/19139 PCT~S96/18701 based on the total weight of resin solids in the coating composition.
The coating composition can contain other optional ingredients, such as co-reactive resinous materials;
plasticizers; anti-oxidants; W light absorbers; surfactants;
flow control agents; anti-settling agents; and the like. When present, these materials are generally used at a level up to 25 percent, preferably up to 10 percent by weight, the percentages based on the total weight of resin solids in the coating composition.
The film-forming composition can be applied to any of the various substrates to which it adheres. Specific examples of suitable substrates include metals, wood, glass, cloth, plastic, foam, elastomeric substrates, and the like.
Typically, the substrate is metal or plastic. Optionally, the substrate could have been previously coated with a primer coating composition, or with a pigmented basecoat and the film-forming composition of the present invention applied as a clear coat over the pigmented base coat to form a color plu~
clear composite coating.
The composition~ can be applied by conventional means including brushing, dipping, flow coating, spraying, and the like. Preferably, they are applied by spraying. The usual spray techniques and equipment ~or air-spraying or electrosta~ic spraying can be used.
When the ~ilm-forming composition is used as a clear coat in a color plu~ clear composite coating, pigmented base coat is first applied to a substrate at a uniform fllm thickness of from about 0.25 to about 1.5 mils. The base coat is then ~lashed," that is, it is left to stand at temperatures ranging from the ambient temperature to 80~C for about 10 seconds to 30 minutes, before another coating composition is CA 02231~39 1998-04-02 WO97/19139 PCT~US96/18701 applied to it. Then, typically, the clear coating composition o~ the present invention is applied over the coated substrate - in one or more coats to a uni~orm ~ilm thickness ~rom 0.5 to 5.0 mils. The substrate is then ~lashed again and ~inally S baked until the ~ilm i8 cured, typically ~or about 20 minutes to about 40 minutes at ~rom about 100~C to about 200~C to produce the coated article.
The base coating compositions are those well known in the art as described, ~or example, in U.S. Patent No. 4,681,811, column l, line 56 to column 4, line 2.
Illustrating the invention are the ~ollowing examples that are not to be considered as limiting the invention to their details. All parts and percentages in the examples as well as throughout the speci~ication are by weight unless otherwise indicated.
MPT.~ A
A hydroxyl ~unctional acrylic copolymer was prepared ~rom the ~ollowing ingredients:
Ingr~l; ~ntS Weight in parts Tn; tiAl ~h~rge xylene lO.7 SO~VESSO lool lO.7 isobutanol 4 3 ~h A rge I
hydroxypropyl acrylate 40.0 butyl methacrylate l9.0 butyl acrylate l9.0 styrene 20.0 30 acrylic acid 2.0 t-dodecyl mercaptan 0.5 1 aromatic ~olvent mixture available ~rom ~xxon Chemical Co WO97/19139 PCT~US96/18701 ~h~rge II
Tngr~;~nts Weight in parts xylene 8.7 SOLVESSO l00 6.4 S VAZO 672 5 o ~h~rge III
SOLVESSO lO0 l.l VAZO 67 0.4 ~h~rge IV
10 SOLVESSO lOO l.l VAZO 67 0.4 The initial charge was added to a 5-liter round bottom 4-neck ~lask equipped with mechanical agitation, nitrogen inlet, reflux c~n~er, and two dropping ~unnels. The charge was heated under a nitrogen ~lanket to re~lux (115~C). At re~lux, Charges I and II were simultaneously and uniformly added over a two hour period maintaining re~lux conditions. Upon completion o~ Charges I and II, Charge III was added and the reaction held ~or one hour. Charge IV was added and the reaction held one more hour. The polymer was characterized as having 69~ solids, hydroxy value o~ 95, and peak molecular weight o~ 7000 ~MPTR B
A c~rh~m~te ~unctional polyester polymer was prepared ~rom the ~ollowing ingredients:
22,2'-dimethylazobi~(isobutyronitrile) available from E~.I du l?ont de Nemourl3 & Co., Inc .
Tngre~;~nts Weight in ~arts 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3- 196.8 hydroxypropyl propionate deionized H2O lO.O
5 trimethylolpropane 42.9 ~utyl ~tannoic acid 0.6 triphenylphosphite 0.8 deionized X2O 3 0 methylhexahydrophth~lic anhydride158.3 10 deioni~ed H2O lO.O
butyl stannoic acid 0 5 triphenylphosphite 0 5 DOWANOL PM 2.0 }5DOWANOL PM r~rh~mfte (37~ solution in DOWANOL PM)4 318.9 DOWANOL PM 10.0 DOWANOL PM 105.0 The first ingredient was charged to a suitable reactor equipped with a glycol recovery column. Deionized H2O
was added to the reactor as a rinse for the first ingredient.
Trimethylolpropane, butyl stannoic acid, and triphenylphosphite were then added to the reactor, followed by a deionized H2O rinse. Methylh~hydrophthalic anhydride, with a subsequent deionized H2O rinse, was then added to the reactor followed by heating the reaction mlxture to 77~C and sparging with nitrogen for 20 minutes. The reaction mixture temperature was then raised to 210~C and H2O was removed from the reactor with the nitrogen sparge. The reaction was continued until an acid value of 10.2 was obtained and the batch was then cooled to 140 C. The intermediate resin had a hydroxyl value of 156.6. DOWANOL PM and butyl stannoic acid were added to the reactor as a slurry, followed by addition of -3 1-methoxy-2-propanol avallable ~rom DOW rh~m;rAl Co.
4 ~ n product oî DOWANOL PM and urea CA 02231~39 1998-04-02 triphenylphosphite and a DOWANOL PM rinse. The DOWANOL PM
carbamate solution was then added to the reactor over a period of 4 hours. During the addition, DOWANOL PM was distilled from the reactor under reduced pressure. Upon completion of the addition of the DOWANOL PM carbamate solution a DOWANOL PM
rinse was added to the reactor. The reaction was continued until DOWANOL PM evolution stopped. A sample of resin (90 parts by weight) was removed from the reactor; the r~m~;ning resin was diluted with DOWANOL PM. The resin prior to dilution had a residual hydroxyl value of 19.4 and an acid value of 8.5. After dilution, the resin had a measured solids content of 71.2~ and a Gardner-Holt viscosity of Z1+. The carbamate functional polyester polymer had an Mn (number average molecular weight) of 720 and an Mw (weight average molecular weight) of 2220 as determined by gel permeation chromatography using a polystyrene st~n~rd.
~MPT-~ C [Com,~ tive) A carbamate functional acrylic polymer was prepared from the following ingredients:
CA 0223l~39 l998-04-02 WO97/19l39PCTrUS96/18701 I~gre~;~nt Weight ~n p~rtS
EXXATE 6005 478.4 butyl acetate 478.4 LUPERSOL 555M606 63.98 S EXXATE 600 11.20 butyl acetate 11.20 hydroxypropyl acrylate 512.00 butyl methacrylate 742.40 methyl styrene dimer 25.60 l0 EXXATE 600 64.00 butyl acetate 64.00 LUPERSOL s55M6o 21.33 EXXATE 600 11.20 butyl acetate 11.20 15 butyl stannoic acid 2.55 triphenylphosphite 2.55 DOWANOL PM carbamate l37~ solution in DOWANOL PM) 1413.74 DOWANOL PM 314.00 ethyl-3-ethoxypropionate 314.00 The first two ingredients were charged to a suitable reactor under a nitrogen blanket and heated to reflux. The next three ingredients were mixed together and added to the reactor at a constant rate over 3.5 hours. Addition o~ a mixture of hydroxypropyl acrylate, butyl methacrylate, methyl 25 styrene dimer, BXXATB 600, and butyl acetate was begun 15 minutes after the beginning of the ~irst addition and added at a constant rate over 3 hours. After completion o~ the above additions the reaction was held at reflux for 1 hour. The next three ingredients were then added to the reactor over a period o~ 0.5 hour. The reaction was continued at reflux for a period o~ 2 hours. Solvent was then removed ~rom the reaction mixture under reduced pressure, ~ollowed by the -Oxo-hexylArr~Atr~ available ~rom Exxon Co.
6 t-a~yl peroxyacetate available ~rom Atochem North America CA 02231~39 1998-04-02 WO97/19139 PCT~US96/18701 addition of the next two ingredients to the reactor. DOWANOL
PM c~rh~te in DOWANOL PM solution was then added to the reactor over a period of 3 hours. During the addition, DOWANOL PM was removed ~rom the reactor under reduced pres~ure. The reaction was continued under reduced pressure until DOWANOL PM evolution stopped. The resin prior to dilution had a residual hydroxyl value o~ 30.6. The resin was diluted with the last two ingredients. After dilution, the resin had a measured solids content of 69.2~, a Gardner-Holt viscosity of Z2-, a number average molecular weight of 3311, and a weight average molecular weight of 7851 as determined by gel permeation chromatography using a polystyrene st~n~rd.
The following examples (1-9) show the preparation of various clear film-forming compositions prepared with the polymers of Examples A, B, and C and aminoplast curing agent.
The clear film-forming compositions were evaluated a~
clearcoats in composite color-plus-clear coatings.
R~MPT~ 1 (Com~r~tive) A clear film-forming composition was prepared by mixing together the ~ollowing ingredients:
WO 97/19139 PCT~US96/18701 Tr~çrr~-~;~ntSolid weight in gr~mc~ Soluti~n weight in gr~m~
n-amyl propionate --- 31.6 methyl n-amyl ketone --- 21.0 'l'lNUVlN 3287 l.5 l.5 5 'l'lNUVlN 9008l. 5 l.5 polybutylacrylate 0.4 0.7 TIN WIN 1239l.O l.O
CYMEL 11301~35.0 35 O
hydroxyl functional acrylic 10 o~ EXAMPLE A65.O 92.9 Neutralized DDBSAll 0.55 l.8 The clear film-forming composition had a hydroxyl value of 85.3 based on total weight of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. B was 100/0 in the clear film-forming composition.
~p~PT.~ 2 A clear film-forming composition was prepared by mixing together the following ingredients:
7 Substituted benzor~; ~7~1 ~ W light sr~h;l; 7~ availahle from Ciba Geigy Corporation 8 Substituted benzotriazole W light st~bilizer available from Ciba Geigy Corporation ~ 9 Sterically hindered amine light s~h;l; 7~ available ~rom Ciba Geigy Corporation lO A fully alkylated, mixed methoxy / butoxy ~unctional ~n~ t resin available ~rom CY~EC Industries.
ll Diisopropanol amine neutralized dodecyl benzene sul~onic aci.~ s~l~l~;~n WO97/19139 PCT~US96/18701 Tngre~;~nt Soli~ weight in gr~mq Solution weight in grAm.
n-amyl propionate --- 31.1 methyl n-amyl ketone --- 18 5 'l'lNUVlN 328 1.5 1.5 'l'lNUVlN 900 1. 5 1.5 polybutylacrylate0.4 0.7 'l'lNUVlN 123 1.0 1.0 CYMEL 1130 35.o 35 0 hydroxyl functional acrylic 10 0~ EXAMPLE A 48.8 69.7 cA~hA~te functional polyester of EXAMPLE B 16.2 21.2 Neutralized DDBSA0.55 1.8 The clear film-forming composition had a hydroxyl value of 67.0 based on total weight of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. B was 75/25 in the clear film-forming composition.
~PT.~ 3 A clear film-forming composition was prepared by mixing together the following ingredients:
Tn~re~;~nt Solid weight in gr~m~ Solutio~ weiaht in gr~
n-amyl propionate --- 36.6 methyl n-amyl ketone --- 12.5 25 'l'lNUVlN 328 1.5 1.5 TINW IN 900 1.5 1.5 polybutylacrylate0.4 0.7 'l'lNUVlN 123 1.0 1.0 CYMEL 1130 35.o 35.o hydroxyl ~unctional acrylic 0~ EXAMPLE A 32.5 46.4 cA~h~m~te ~unctional polyester of EXAMPLE B 32.5 43.0 Neutralized DDBSA 0.55 1.8 The clear film-forming composition had a hydroxyl value of 48.6 based on total weight of resin solids in the clear WO97/19139 PCT~US96/18701 film-forming composition. The solid resin weight ratio of Ex.
A to Ex. B was 50/50 in the clear film-forming composition.
.MpT.h: 4 A clear film-forming composition was prepared by mixing together the following ingredients:
Tngre~;~nt Solid weight in grAm~ 5Olution weight in gr~m.q n-amyl propionate --- 39.0 methyl n-amyl ketone --- 8.0 0 'l'lNUVlN 328 1.5 1.5 'l'lNUVlN 900 1. 5 1.5 polybutylacrylate 0.4 o 7 'l'LNUVlN 123 l.O l.O
CYMEL 1130 35.0 35 o hydroxyl functional acrylic of EXAMPLE A 16.2 22.9 cA~hAmAte functional polyester of EXAMPLE B 48.8 64.6 Neutralized DDBSAO . 55 1.8 The clear film-forming composition had a hydroxyl value of 3û.3 based on total weight of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. B was 25/75 in the clear film-forming composition.
R~MPL~ 5 (Co~p~r~tive) A clear film-forming composition was prepared by mixing together the ~ollowing ingredients:
WO97/19139 PCT~US96/18701 Tngre~;ent Soli~ wei~t in ar~m~ Sslution wei~ht in gr~mq n-amyl propionate --- 44 4 methyl n-amyl ketone --- 2.0 'l'lNUVlN 328 1.5 1.5 S 'l'lNUVlN 900 1. 5 1.5 polybutylacrylate0.4 o 7 'l'lNUVlN 123 l.O l.O
CYMEL 1130 35.0 35 o ~h~m~te functional 10 polyester of EXAMPLE B 6s.0 86.1 Neutralized DDBSA0.55 1.8 The clear ~ilm-forming composition had a hydroxyl value of 12.0 based on total weiyht of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. B was O/lOO in the clear film-forming composition.
E~MPT,R 6 (Co~tive~
A clear film-forming composition was prepared by mixing together the following ingredients:
20 Tnyre~; ~nt Solid weight ;n gr~mcs Soluti--n weight ;n gX;-m n-amyl propionate --- 31.1 methyl n-amyl ketone --- 22.0 'l'lNUVlN 328 1.5 1.5 'l'lNUVlN 900 1.5 1.5 25 polybutylacrylate0.4 0.7 l~lNUVlN 123 l.O 1.O
CYMEL 1130 35.o 3s.0 hydroxyl functional acrylic of EXAMPLE A 48.8 69.7 30 carbamate functional acrylic of EXAMPLE C 16.2 a4.7 Neutralized DDBSA0.55 1.8 The clear film-forming composition had a hydroxyl value of 68.7 based on total weight of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. C was 75/25 in the clear ~ilm-forming composition.
CA 0223l539 l998-04-02 WO97/19139 PCT~S96/18701 ~PT .~. 7 ( Corn,~ r~ t ive) A clear film-forming composition was prepared by mixing together the following ingredients:
5 Ingre~;~nt Solid weight in gr~m.q Soluti~n wei~ht in gramq n-amyl propionate --- 29.5 methyl n-amyl ketone --- 22.0 'l'lNUVlN 328 1.5 1.5 TINWIN goo 1.5 1.5 10 polybutylacrylate o 4 0 7 TINWIN 123 1.O l.O
CYMEL 1130 35.o 35 o hydroxyl functional acrylic o~ EXAMPLE A 32.5 46.4 15 c~r~m Ite ~unctional acrylic of EXAMPLE C 32.5 49.6 Neutralized DDBSAO . 55 1.8 The clear film-forming composition had a hydroxyl value of 52.1 based on total weight of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. C was 50/50 in the clear film-forming composition.
R~PT,~ 8 (Co~rative) A clear film-forming composition was prepared by mixing together the following ingredients:
T~gr~;~nt Soli~ weight in gr~mq Solutio~ weight in gr~mq n-amyl propionate --- 28.6 methyl n-amyl ketone --- 22.5 l'lNUVlN 328 1.5 1.5 llNUVlN 900 1.5 1.5 polybutylacrylateO. 4 0.7 LlNUVlN 123 1.0 1.0 CYMEL 1130 35.0 35 0 hydroxyl ~unctional acrylic 10 o~ EXAMPLE A 16.2 22.9 ~h~m~te ~unctional acrylic of EXAMPLE C 48.8 74.5 Neutralized DDBSA0.55 1.8 The clear film-forming composition had a hydroxyl value of 3S.4 based on total weight of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. C was 25/75 in the clear film-forming composition.
~MPT.R ~ (C~m~ tive) A clear film-forming composition was prepared by mixing together the following ingredients:
In~r~;ent Solid weight in gr~mq Solution weight in gr~mq n-amyl propionate --- 27.8 methyl n-amyl ketone --- 23.5 25 TINUVIN 328 1.5 1.5 llNUVlN 900 1.5 1.5 polybutylacrylate0.4 o. 7 uvlN 123 1.0 1.0 CYMEL 1130 35.0 35.0 carbamate ~unctional acrylic of EXAMPLE C 65.0 99.2 Neutralized DDBSA0.55 1.8 The clear film-forming composition had a hydroxyl value of l9.0 based on total weight of resin solids in the clear CA 02231~39 1998-04-02 WO97/19139 PCT~S96/18701 film-forming composition. The solid resin weight ratio of Ex.
A to Ex. C was 0/l00 in the clear film-forming composition.
The film-forming compositions of Examples l-9 were - S applied to pigmented basecoats to form color-plus-clear composite coatings over cured electrocoated steel substrates.
The basecoats used for examples 1-9 are commercially available from PPG Industries, Inc. and are identified as DCT-6373 (black in color) and DCT-6612 (pumice metallic!. The electrocoat used on the steel is commercially available from PPG Industries, Inc. and is identified as ED-5000.
The basecoat was spray applied in two coats to electrocoated steel panels at a temperature of about 75~F
(24~C). Approximately a 15 second flash time was allowed between the two basecoat applications. After the second basecoat application, a flash time of 5 to 15 minutes was allowed at 75~F (24~C) before the application of the clear coating composition. The clear coating compositions of Examples l-9 were each applied to a basecoated panel in two coats with a ninety second flash at 75~F (24~C) allowed between coats The composite coating wa~ allowed to air flash at 75~E
(24~C) for l0 minutes before baking at 285~F (141~C) to cure both the basecoat and the clearcoat. The panels were baked in a horizontal position. One black and one pumice colored panel for each clearcoat example was baked for 25 minutes and used to test appearance, acid etch resistance, and humidity resistance. In order to test recoat adhesion of the clearcoat examples, a second black colored panel for each clearcoat example was prepared using the identical application procedure described above, however these panels were baked for one hour at 285~F (141~C), to cure both the basecoat and the clearcoat.
After the hour bake, each panel was allowed to cool, and then CA 02231~39 1998-04-02 WO97/19139 PCT~US96/18701 the same clearcoat example was reapplied directly to the surface of the ~irst fully-cured clearcoat without sanding or applying a~ additional layer o~ basecoat. The panels were then baked ~or 25 minutes at 285~F (141~C) to cure the additional layer of clearcoat. The purpose of the longer bake time on the first coat of basecoat and clearcoat was to increase the severity of a~lesion ~ailure between the two separately cured layers of clearcoat. The results ~or acid etch resistance and recoat adhesion over black basecoat, and appearance and humidity resistance over pumice metallic basecoat are shown in Table 1.
WO 97/19139 PCT~US96/18701 ~ ~ ul + Ul Ul ~n + c~ ,1 0 C) ~
~o o o ~ o o ~o ~o ,-- o o o , , o o o o O H ~ ~'I ~ 117 ~0 ~r ~ a~ O
_I O
O ~ 111d' a~
3 I N ~ U~ o~
_1 14 E~
.J ~ U V V
O ~ V U V
C
P~ ~ ~,~
~ 0~ 0~
O O O O O O
O U U U U U V
U ~ U V ) V V V U
u~ o In ) In o In ~
v ul o Lr O In o u~ V
#
CA 02231~39 1998-04-02 WO 97/19139 PCT~US96/18701 1A solution of 350 parts deionized water and 12 par~6 gulfurous acid wa~ prepared. The acid solution was sprayed onto the panels using a polyethylene spray bottle, giving a distribution of drop sizes up to one ~uarter inch Approximately 1.5 grams of solution was applied per 2x4 inch panel. The panels were then placed in an oven at 120~F (49~C) for t~enty m;nllt~R. The panels were removed from the oven and the spray/bake procedure was repeated two more times to give a total of 60 ~;nllt~ at 120~F (49~C).
After the third cycle the panels were washed with soap and water and dried, then rated for acid etch resi~tance on a scale of O-lO based on standard test panels (O s no observable etch; lO = severe etching).
2200 glos6 measured by a Glossgard II glossmeter from Pacific Scientific. DOI (distinction of image) measured usiny a Dorigon II DOI
meter from ~unter La~.
Ten day8 exposure at 110~F on a QCT con~n~ation te8ter (Q-Panel Company; Cleveland, OH). Panels were rated for blushing and ~listering.
Blush was rated on a scale of O to 5 (o = no ~lush or color change, 5 =
severe blush or colo~ change.
Recoat adhesion performed on panels c~nt~ning two separately applied and baked layers of clearcoat as described in the panel preparation section A &esion tested using a model P~A-T paint adhesion test kit from Paul N
Gardner Company, Inc. equipped with a multiple tip cutter c~nt~;n;ng eleven teeth with 1.O mm spacing. The panels were scribed according to ASTM-3359 and then Scotch Brand "898~ tape from 3M Corporation was applied to the scribed area and then removed firmly in attempt to pull any loose paint from the panel. The A~h~i~n was then rated according to ASTM-3359 (O = no adhesion, 5 = perfect adhesion).
The data summarized in Table 1 shows that the all acrylic polyol system (Ex. 1) although having excellent appearance, humidity resistance, and recoat adhesion, has poor acid etch resistance. Blending the acrylic polyol with polyester carbamate within the range of 75/25 to 25/75 (Examples 2-4) dramatically improves the acid etch resistance while maint~;nlng the other properties shown in the Table 1. When the polyester carbamate level reaches 75~ (Ex. 4) and greater (Ex. 5) the humidity resistance suffers. Blending of the acrylic polyol with acrylic carbamate (Examples 6-8) although CA 0223l539 l998-04-02 WO97/19139 PCTrUS96/18701 providing good appearance, humidity resistance, and acid etch resistance results in poor recoat adhesion.
carbamate solution was then added to the reactor over a period of 4 hours. During the addition, DOWANOL PM was distilled from the reactor under reduced pressure. Upon completion of the addition of the DOWANOL PM carbamate solution a DOWANOL PM
rinse was added to the reactor. The reaction was continued until DOWANOL PM evolution stopped. A sample of resin (90 parts by weight) was removed from the reactor; the r~m~;ning resin was diluted with DOWANOL PM. The resin prior to dilution had a residual hydroxyl value of 19.4 and an acid value of 8.5. After dilution, the resin had a measured solids content of 71.2~ and a Gardner-Holt viscosity of Z1+. The carbamate functional polyester polymer had an Mn (number average molecular weight) of 720 and an Mw (weight average molecular weight) of 2220 as determined by gel permeation chromatography using a polystyrene st~n~rd.
~MPT-~ C [Com,~ tive) A carbamate functional acrylic polymer was prepared from the following ingredients:
CA 0223l~39 l998-04-02 WO97/19l39PCTrUS96/18701 I~gre~;~nt Weight ~n p~rtS
EXXATE 6005 478.4 butyl acetate 478.4 LUPERSOL 555M606 63.98 S EXXATE 600 11.20 butyl acetate 11.20 hydroxypropyl acrylate 512.00 butyl methacrylate 742.40 methyl styrene dimer 25.60 l0 EXXATE 600 64.00 butyl acetate 64.00 LUPERSOL s55M6o 21.33 EXXATE 600 11.20 butyl acetate 11.20 15 butyl stannoic acid 2.55 triphenylphosphite 2.55 DOWANOL PM carbamate l37~ solution in DOWANOL PM) 1413.74 DOWANOL PM 314.00 ethyl-3-ethoxypropionate 314.00 The first two ingredients were charged to a suitable reactor under a nitrogen blanket and heated to reflux. The next three ingredients were mixed together and added to the reactor at a constant rate over 3.5 hours. Addition o~ a mixture of hydroxypropyl acrylate, butyl methacrylate, methyl 25 styrene dimer, BXXATB 600, and butyl acetate was begun 15 minutes after the beginning of the ~irst addition and added at a constant rate over 3 hours. After completion o~ the above additions the reaction was held at reflux for 1 hour. The next three ingredients were then added to the reactor over a period o~ 0.5 hour. The reaction was continued at reflux for a period o~ 2 hours. Solvent was then removed ~rom the reaction mixture under reduced pressure, ~ollowed by the -Oxo-hexylArr~Atr~ available ~rom Exxon Co.
6 t-a~yl peroxyacetate available ~rom Atochem North America CA 02231~39 1998-04-02 WO97/19139 PCT~US96/18701 addition of the next two ingredients to the reactor. DOWANOL
PM c~rh~te in DOWANOL PM solution was then added to the reactor over a period of 3 hours. During the addition, DOWANOL PM was removed ~rom the reactor under reduced pres~ure. The reaction was continued under reduced pressure until DOWANOL PM evolution stopped. The resin prior to dilution had a residual hydroxyl value o~ 30.6. The resin was diluted with the last two ingredients. After dilution, the resin had a measured solids content of 69.2~, a Gardner-Holt viscosity of Z2-, a number average molecular weight of 3311, and a weight average molecular weight of 7851 as determined by gel permeation chromatography using a polystyrene st~n~rd.
The following examples (1-9) show the preparation of various clear film-forming compositions prepared with the polymers of Examples A, B, and C and aminoplast curing agent.
The clear film-forming compositions were evaluated a~
clearcoats in composite color-plus-clear coatings.
R~MPT~ 1 (Com~r~tive) A clear film-forming composition was prepared by mixing together the ~ollowing ingredients:
WO 97/19139 PCT~US96/18701 Tr~çrr~-~;~ntSolid weight in gr~mc~ Soluti~n weight in gr~m~
n-amyl propionate --- 31.6 methyl n-amyl ketone --- 21.0 'l'lNUVlN 3287 l.5 l.5 5 'l'lNUVlN 9008l. 5 l.5 polybutylacrylate 0.4 0.7 TIN WIN 1239l.O l.O
CYMEL 11301~35.0 35 O
hydroxyl functional acrylic 10 o~ EXAMPLE A65.O 92.9 Neutralized DDBSAll 0.55 l.8 The clear film-forming composition had a hydroxyl value of 85.3 based on total weight of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. B was 100/0 in the clear film-forming composition.
~p~PT.~ 2 A clear film-forming composition was prepared by mixing together the following ingredients:
7 Substituted benzor~; ~7~1 ~ W light sr~h;l; 7~ availahle from Ciba Geigy Corporation 8 Substituted benzotriazole W light st~bilizer available from Ciba Geigy Corporation ~ 9 Sterically hindered amine light s~h;l; 7~ available ~rom Ciba Geigy Corporation lO A fully alkylated, mixed methoxy / butoxy ~unctional ~n~ t resin available ~rom CY~EC Industries.
ll Diisopropanol amine neutralized dodecyl benzene sul~onic aci.~ s~l~l~;~n WO97/19139 PCT~US96/18701 Tngre~;~nt Soli~ weight in gr~mq Solution weight in grAm.
n-amyl propionate --- 31.1 methyl n-amyl ketone --- 18 5 'l'lNUVlN 328 1.5 1.5 'l'lNUVlN 900 1. 5 1.5 polybutylacrylate0.4 0.7 'l'lNUVlN 123 1.0 1.0 CYMEL 1130 35.o 35 0 hydroxyl functional acrylic 10 0~ EXAMPLE A 48.8 69.7 cA~hA~te functional polyester of EXAMPLE B 16.2 21.2 Neutralized DDBSA0.55 1.8 The clear film-forming composition had a hydroxyl value of 67.0 based on total weight of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. B was 75/25 in the clear film-forming composition.
~PT.~ 3 A clear film-forming composition was prepared by mixing together the following ingredients:
Tn~re~;~nt Solid weight in gr~m~ Solutio~ weiaht in gr~
n-amyl propionate --- 36.6 methyl n-amyl ketone --- 12.5 25 'l'lNUVlN 328 1.5 1.5 TINW IN 900 1.5 1.5 polybutylacrylate0.4 0.7 'l'lNUVlN 123 1.0 1.0 CYMEL 1130 35.o 35.o hydroxyl ~unctional acrylic 0~ EXAMPLE A 32.5 46.4 cA~h~m~te ~unctional polyester of EXAMPLE B 32.5 43.0 Neutralized DDBSA 0.55 1.8 The clear film-forming composition had a hydroxyl value of 48.6 based on total weight of resin solids in the clear WO97/19139 PCT~US96/18701 film-forming composition. The solid resin weight ratio of Ex.
A to Ex. B was 50/50 in the clear film-forming composition.
.MpT.h: 4 A clear film-forming composition was prepared by mixing together the following ingredients:
Tngre~;~nt Solid weight in grAm~ 5Olution weight in gr~m.q n-amyl propionate --- 39.0 methyl n-amyl ketone --- 8.0 0 'l'lNUVlN 328 1.5 1.5 'l'lNUVlN 900 1. 5 1.5 polybutylacrylate 0.4 o 7 'l'LNUVlN 123 l.O l.O
CYMEL 1130 35.0 35 o hydroxyl functional acrylic of EXAMPLE A 16.2 22.9 cA~hAmAte functional polyester of EXAMPLE B 48.8 64.6 Neutralized DDBSAO . 55 1.8 The clear film-forming composition had a hydroxyl value of 3û.3 based on total weight of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. B was 25/75 in the clear film-forming composition.
R~MPL~ 5 (Co~p~r~tive) A clear film-forming composition was prepared by mixing together the ~ollowing ingredients:
WO97/19139 PCT~US96/18701 Tngre~;ent Soli~ wei~t in ar~m~ Sslution wei~ht in gr~mq n-amyl propionate --- 44 4 methyl n-amyl ketone --- 2.0 'l'lNUVlN 328 1.5 1.5 S 'l'lNUVlN 900 1. 5 1.5 polybutylacrylate0.4 o 7 'l'lNUVlN 123 l.O l.O
CYMEL 1130 35.0 35 o ~h~m~te functional 10 polyester of EXAMPLE B 6s.0 86.1 Neutralized DDBSA0.55 1.8 The clear ~ilm-forming composition had a hydroxyl value of 12.0 based on total weiyht of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. B was O/lOO in the clear film-forming composition.
E~MPT,R 6 (Co~tive~
A clear film-forming composition was prepared by mixing together the following ingredients:
20 Tnyre~; ~nt Solid weight ;n gr~mcs Soluti--n weight ;n gX;-m n-amyl propionate --- 31.1 methyl n-amyl ketone --- 22.0 'l'lNUVlN 328 1.5 1.5 'l'lNUVlN 900 1.5 1.5 25 polybutylacrylate0.4 0.7 l~lNUVlN 123 l.O 1.O
CYMEL 1130 35.o 3s.0 hydroxyl functional acrylic of EXAMPLE A 48.8 69.7 30 carbamate functional acrylic of EXAMPLE C 16.2 a4.7 Neutralized DDBSA0.55 1.8 The clear film-forming composition had a hydroxyl value of 68.7 based on total weight of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. C was 75/25 in the clear ~ilm-forming composition.
CA 0223l539 l998-04-02 WO97/19139 PCT~S96/18701 ~PT .~. 7 ( Corn,~ r~ t ive) A clear film-forming composition was prepared by mixing together the following ingredients:
5 Ingre~;~nt Solid weight in gr~m.q Soluti~n wei~ht in gramq n-amyl propionate --- 29.5 methyl n-amyl ketone --- 22.0 'l'lNUVlN 328 1.5 1.5 TINWIN goo 1.5 1.5 10 polybutylacrylate o 4 0 7 TINWIN 123 1.O l.O
CYMEL 1130 35.o 35 o hydroxyl functional acrylic o~ EXAMPLE A 32.5 46.4 15 c~r~m Ite ~unctional acrylic of EXAMPLE C 32.5 49.6 Neutralized DDBSAO . 55 1.8 The clear film-forming composition had a hydroxyl value of 52.1 based on total weight of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. C was 50/50 in the clear film-forming composition.
R~PT,~ 8 (Co~rative) A clear film-forming composition was prepared by mixing together the following ingredients:
T~gr~;~nt Soli~ weight in gr~mq Solutio~ weight in gr~mq n-amyl propionate --- 28.6 methyl n-amyl ketone --- 22.5 l'lNUVlN 328 1.5 1.5 llNUVlN 900 1.5 1.5 polybutylacrylateO. 4 0.7 LlNUVlN 123 1.0 1.0 CYMEL 1130 35.0 35 0 hydroxyl ~unctional acrylic 10 o~ EXAMPLE A 16.2 22.9 ~h~m~te ~unctional acrylic of EXAMPLE C 48.8 74.5 Neutralized DDBSA0.55 1.8 The clear film-forming composition had a hydroxyl value of 3S.4 based on total weight of resin solids in the clear film-forming composition. The solid resin weight ratio of Ex.
A to Ex. C was 25/75 in the clear film-forming composition.
~MPT.R ~ (C~m~ tive) A clear film-forming composition was prepared by mixing together the following ingredients:
In~r~;ent Solid weight in gr~mq Solution weight in gr~mq n-amyl propionate --- 27.8 methyl n-amyl ketone --- 23.5 25 TINUVIN 328 1.5 1.5 llNUVlN 900 1.5 1.5 polybutylacrylate0.4 o. 7 uvlN 123 1.0 1.0 CYMEL 1130 35.0 35.0 carbamate ~unctional acrylic of EXAMPLE C 65.0 99.2 Neutralized DDBSA0.55 1.8 The clear film-forming composition had a hydroxyl value of l9.0 based on total weight of resin solids in the clear CA 02231~39 1998-04-02 WO97/19139 PCT~S96/18701 film-forming composition. The solid resin weight ratio of Ex.
A to Ex. C was 0/l00 in the clear film-forming composition.
The film-forming compositions of Examples l-9 were - S applied to pigmented basecoats to form color-plus-clear composite coatings over cured electrocoated steel substrates.
The basecoats used for examples 1-9 are commercially available from PPG Industries, Inc. and are identified as DCT-6373 (black in color) and DCT-6612 (pumice metallic!. The electrocoat used on the steel is commercially available from PPG Industries, Inc. and is identified as ED-5000.
The basecoat was spray applied in two coats to electrocoated steel panels at a temperature of about 75~F
(24~C). Approximately a 15 second flash time was allowed between the two basecoat applications. After the second basecoat application, a flash time of 5 to 15 minutes was allowed at 75~F (24~C) before the application of the clear coating composition. The clear coating compositions of Examples l-9 were each applied to a basecoated panel in two coats with a ninety second flash at 75~F (24~C) allowed between coats The composite coating wa~ allowed to air flash at 75~E
(24~C) for l0 minutes before baking at 285~F (141~C) to cure both the basecoat and the clearcoat. The panels were baked in a horizontal position. One black and one pumice colored panel for each clearcoat example was baked for 25 minutes and used to test appearance, acid etch resistance, and humidity resistance. In order to test recoat adhesion of the clearcoat examples, a second black colored panel for each clearcoat example was prepared using the identical application procedure described above, however these panels were baked for one hour at 285~F (141~C), to cure both the basecoat and the clearcoat.
After the hour bake, each panel was allowed to cool, and then CA 02231~39 1998-04-02 WO97/19139 PCT~US96/18701 the same clearcoat example was reapplied directly to the surface of the ~irst fully-cured clearcoat without sanding or applying a~ additional layer o~ basecoat. The panels were then baked ~or 25 minutes at 285~F (141~C) to cure the additional layer of clearcoat. The purpose of the longer bake time on the first coat of basecoat and clearcoat was to increase the severity of a~lesion ~ailure between the two separately cured layers of clearcoat. The results ~or acid etch resistance and recoat adhesion over black basecoat, and appearance and humidity resistance over pumice metallic basecoat are shown in Table 1.
WO 97/19139 PCT~US96/18701 ~ ~ ul + Ul Ul ~n + c~ ,1 0 C) ~
~o o o ~ o o ~o ~o ,-- o o o , , o o o o O H ~ ~'I ~ 117 ~0 ~r ~ a~ O
_I O
O ~ 111d' a~
3 I N ~ U~ o~
_1 14 E~
.J ~ U V V
O ~ V U V
C
P~ ~ ~,~
~ 0~ 0~
O O O O O O
O U U U U U V
U ~ U V ) V V V U
u~ o In ) In o In ~
v ul o Lr O In o u~ V
#
CA 02231~39 1998-04-02 WO 97/19139 PCT~US96/18701 1A solution of 350 parts deionized water and 12 par~6 gulfurous acid wa~ prepared. The acid solution was sprayed onto the panels using a polyethylene spray bottle, giving a distribution of drop sizes up to one ~uarter inch Approximately 1.5 grams of solution was applied per 2x4 inch panel. The panels were then placed in an oven at 120~F (49~C) for t~enty m;nllt~R. The panels were removed from the oven and the spray/bake procedure was repeated two more times to give a total of 60 ~;nllt~ at 120~F (49~C).
After the third cycle the panels were washed with soap and water and dried, then rated for acid etch resi~tance on a scale of O-lO based on standard test panels (O s no observable etch; lO = severe etching).
2200 glos6 measured by a Glossgard II glossmeter from Pacific Scientific. DOI (distinction of image) measured usiny a Dorigon II DOI
meter from ~unter La~.
Ten day8 exposure at 110~F on a QCT con~n~ation te8ter (Q-Panel Company; Cleveland, OH). Panels were rated for blushing and ~listering.
Blush was rated on a scale of O to 5 (o = no ~lush or color change, 5 =
severe blush or colo~ change.
Recoat adhesion performed on panels c~nt~ning two separately applied and baked layers of clearcoat as described in the panel preparation section A &esion tested using a model P~A-T paint adhesion test kit from Paul N
Gardner Company, Inc. equipped with a multiple tip cutter c~nt~;n;ng eleven teeth with 1.O mm spacing. The panels were scribed according to ASTM-3359 and then Scotch Brand "898~ tape from 3M Corporation was applied to the scribed area and then removed firmly in attempt to pull any loose paint from the panel. The A~h~i~n was then rated according to ASTM-3359 (O = no adhesion, 5 = perfect adhesion).
The data summarized in Table 1 shows that the all acrylic polyol system (Ex. 1) although having excellent appearance, humidity resistance, and recoat adhesion, has poor acid etch resistance. Blending the acrylic polyol with polyester carbamate within the range of 75/25 to 25/75 (Examples 2-4) dramatically improves the acid etch resistance while maint~;nlng the other properties shown in the Table 1. When the polyester carbamate level reaches 75~ (Ex. 4) and greater (Ex. 5) the humidity resistance suffers. Blending of the acrylic polyol with acrylic carbamate (Examples 6-8) although CA 0223l539 l998-04-02 WO97/19139 PCTrUS96/18701 providing good appearance, humidity resistance, and acid etch resistance results in poor recoat adhesion.
Claims (39)
1. An adherent film-forming composition comprising:
(a) 25 to 70 percent by weight of a polymer or oligomer containing repeating ester groups in the polymer or oligomer backbone and containing a plurality of terminal carbamate groups of the structure:
(b) 30 to 75 percent by weight of a hydroxyl functional polymer derived from ethylenically unsaturated monomers; and (c) 25 to 50 percent by weight of an aminoplast crosslinking agent;
the percentages by weight of (a) and (b) being based on total resin solids weight of (a) plus (b); the percentage by weight of (c) being based on total weight of resin solids in the film-forming composition.
(a) 25 to 70 percent by weight of a polymer or oligomer containing repeating ester groups in the polymer or oligomer backbone and containing a plurality of terminal carbamate groups of the structure:
(b) 30 to 75 percent by weight of a hydroxyl functional polymer derived from ethylenically unsaturated monomers; and (c) 25 to 50 percent by weight of an aminoplast crosslinking agent;
the percentages by weight of (a) and (b) being based on total resin solids weight of (a) plus (b); the percentage by weight of (c) being based on total weight of resin solids in the film-forming composition.
2. The film-forming composition of claim 1 in which the percentage by weight of (a) plus (b) is from 25 to 75 percent by weight based on total weight of resin solids in the film-forming composition.
3. The composition of claim 1 in which the polymer or oligomer (a) is a polyester which is the reaction product of an organic polycarboxylic acid or anhydride and a mixture of at least one diol and at least one triol.
4. The composition of claim 3 in which the polyester is prepared from a mixture of at least one diol and at least one triol and the mole ratio of triol to diol is less than 3.3:1.
5. The composition of claim 4 in which the diol is 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate and the triol is trimethylol propane.
6. The film-forming composition of claim 1 in which the polymer or oligomer (a) has an equivalent weight of up to 2500 based on equivalents of terminal carbamate functional groups.
7. The film-forming composition of claim 1 in which the polymer or oligomer (a) has a weight average molecular weight of from 1000 to 30,000, as determined by gel permeation chromatography using polystyrene as a standard.
8. The film-forming composition of claim 1 in which the hydroxyl functional polymer is represented by randomly repeating units according to the following formula:
where R is H or CH3; Q is a divalent linking group; Z is a repeating unit derived from one or more polymerizable ethylenically unsaturated monomers; and x, on a weight basis, is 30 to 70 percent and y, on a weight basis, is 30 to 70 percent, with the percentage of x plus y being equal to 100 percent.
where R is H or CH3; Q is a divalent linking group; Z is a repeating unit derived from one or more polymerizable ethylenically unsaturated monomers; and x, on a weight basis, is 30 to 70 percent and y, on a weight basis, is 30 to 70 percent, with the percentage of x plus y being equal to 100 percent.
9. The hydroxyl functional polymer of claim 8 in which the divalent linking group Q is -COO-Q' where Q' is a divalent aliphatic linking group of 2 to 8 carbon atoms.
10. The film-forming composition of claim 1 in which the hydroxyl functional polymer derived from ethylenically unsaturated monomers is a hydroxyl functional acrylic copolymer of one or more hydroxyalkyl esters of acrylic acid or methacrylic acid and one or more other ethylenically unsaturated monomers.
11. The hydroxyl functional acrylic polymer of claim 10 in which the hydroxyalkyl esters of acrylic acid or methacrylic acid are selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
12. The film-forming composition of claim 1 in which the hydroxyl functional polymer has an equivalent weight of up to 2500 based on equivalents of hydroxyl groups.
13. The film-forming composition of claim 1 in which the hydroxyl functional polymer has a weight average molecular weight of from about 1000 to 30,000 as determined by gel permeation chromatography using polystyrene as a standard.
14. The film-forming composition of claim 1 in which the aminoplast is a condensate of melamine with formaldehyde and an alcohol containing from 1 to 6 carbon atoms.
15. The film-forming composition of claim 14 in which the alcohol is selected from the group consisting of methanol, butanol and mixtures thereof.
16. The film-forming composition of claim 14 in which the aminoplast crosslinking agent is fully alkylated.
17. The film-forming composition of claim 1 which has a hydroxyl value of less than 70 based on total weight of resin solids in the film-forming composition.
18. An adherent clear film-forming composition comprising:
(a) 40 to 60 percent by weight of a polymer or oligomer containing repeating ester groups in the polymer or oligomer backbone and containing a plurality of terminal carbamate groups of the structure:
(b) 40 to 60 percent by weight of a hydroxyl functional acrylic copolymer; and (c) 25 to 50 percent by weight of a fully alkylated aminoplast crosslinking agent;
the percentages by weight of (a) and (b) being based on total resin solids weight of (a) plus (b); the percentage by weight of (c) being based on total weight of resin solids in the film-forming composition.
(a) 40 to 60 percent by weight of a polymer or oligomer containing repeating ester groups in the polymer or oligomer backbone and containing a plurality of terminal carbamate groups of the structure:
(b) 40 to 60 percent by weight of a hydroxyl functional acrylic copolymer; and (c) 25 to 50 percent by weight of a fully alkylated aminoplast crosslinking agent;
the percentages by weight of (a) and (b) being based on total resin solids weight of (a) plus (b); the percentage by weight of (c) being based on total weight of resin solids in the film-forming composition.
19. A method of applying a composite coating to a substrate comprising:
(a) applying to the substrate a colored film-forming composition to form a base coat and (b) applying to said base coat a clear film-forming composition to form a transparent top coat over the base coat wherein the clear film-forming composition comprises:
(i) 25 to 70 percent by weight of a polymer or oligomer containing repeating ester groups in the polymer or oligomer backbone and containing a plurality of terminal carbamate groups of the structure:
(ii) 30 to 75 percent by weight of a hydroxyl functional polymer derived from ethylenically unsaturated monomers;
(iii) 25 to 50 percent by weight of an aminoplast crosslinking agent having a plurality of functional groups that are reactive with said terminal groups of (i);
the percentages by weight of (i) and (ii) being based on total resin solids weight of (i) plus (ii); the percentage by weight of (iii) being based on total weight of resin solids in the clear film-forming composition.
(a) applying to the substrate a colored film-forming composition to form a base coat and (b) applying to said base coat a clear film-forming composition to form a transparent top coat over the base coat wherein the clear film-forming composition comprises:
(i) 25 to 70 percent by weight of a polymer or oligomer containing repeating ester groups in the polymer or oligomer backbone and containing a plurality of terminal carbamate groups of the structure:
(ii) 30 to 75 percent by weight of a hydroxyl functional polymer derived from ethylenically unsaturated monomers;
(iii) 25 to 50 percent by weight of an aminoplast crosslinking agent having a plurality of functional groups that are reactive with said terminal groups of (i);
the percentages by weight of (i) and (ii) being based on total resin solids weight of (i) plus (ii); the percentage by weight of (iii) being based on total weight of resin solids in the clear film-forming composition.
20. A method of repairing a color plus clear composite coating comprising locating an area of the composite coating which is flawed, applying a clear film-forming composition to said flawed area after the flawed area has been prepared for recoating, wherein the clear film-forming composition comprises:
(i) 25 to 70 percent by weight of a polymer or oligomer containing repeating ester groups in the polymer or oligomer backbone and containing a plurality of terminal carbamate groups of the structure:
(ii) 30 to 75 percent by weight of an hydroxyl functional polymer derived from ethylenically unsaturated monomers; and (iii) 25 to 50 percent by weight of a fully alkylated aminoplast crosslinking agent;
the percentages by weight of (i) and (ii) being based on total resin solids weight of (i) plus (ii); the percentage by weight of (iii) being based on total weight of resin solids in the clear film-forming composition.
(i) 25 to 70 percent by weight of a polymer or oligomer containing repeating ester groups in the polymer or oligomer backbone and containing a plurality of terminal carbamate groups of the structure:
(ii) 30 to 75 percent by weight of an hydroxyl functional polymer derived from ethylenically unsaturated monomers; and (iii) 25 to 50 percent by weight of a fully alkylated aminoplast crosslinking agent;
the percentages by weight of (i) and (ii) being based on total resin solids weight of (i) plus (ii); the percentage by weight of (iii) being based on total weight of resin solids in the clear film-forming composition.
21. The method of claim 19 in which the polymer or oligomer (i) is a polyester which is the reaction product of an organic polycarboxylic acid or anhydride and a mixture of at least one diol and at least one triol.
22. The method of claim 21 in which the polyester is prepared from a mixture of at least one diol and at least one triol and the mole ratio of triol to diol is less than 3.3:1.
23. The method of claim 22 in which the diol is 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate and the triol is trimethylolpropane.
24 The method of claim 19 in which the polymer or oligomer (i) has an equivalent weight of up to 2500 based on equivalents of terminal carbamate groups.
25. The method of claim 19 in which the polymer or oligomer (i) has a weight average molecular weight of from 1000 to 30,000 as determined by gel permeation chromatography using polystyrene as a standard.
26. The method of claim 19 in which the hydroxyl functional polymer is represented by randomly repeating units according to the following formula:
where R is H or CH3; Q is a divalent linking group; Z is a repeating unit derived from one or more polymerizable ethylenically unsaturated monomers; and x, on a weight basis, is 30 to 70 percent and y, on a weight basis, is 30 to 70 percent, with the percentage of x plus y being equal to 100 percent.
where R is H or CH3; Q is a divalent linking group; Z is a repeating unit derived from one or more polymerizable ethylenically unsaturated monomers; and x, on a weight basis, is 30 to 70 percent and y, on a weight basis, is 30 to 70 percent, with the percentage of x plus y being equal to 100 percent.
27. The method of claim 26 in which the divalent linking group Y is -COO-Q' where Q' is a divalent aliphatic linking group of 2 to 8 carbon atoms.
28. The method of claim 19 in which the hydroxyl functional polymer derived from ethylenically unsaturated monomers is a hydroxyl functional acrylic copolymer of one or more hydroxyalkyl esters of acrylic acid or methacrylic acid and one or more other ethylenically unsaturated monomers.
29. The method of claim 28 in which the hydroxyalkyl esters of acrylic acid or methacrylic acid are selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
30. The method of claim 19 in which the hydroxyl functional polymer has an equivalent weight of up to 2500 based on equivalents of hydroxyl groups.
31. The method of claim 19 in which the hydroxyl functional polymer has a weight average molecular weight of from about 1000 to 30,000 as determined by gel permeation chromatography using polystyrene as a standard.
32. The method of claim 19 in which the aminoplast is a condensate of melamine with formaldehyde and an alcohol containing from 1 to 6 carbon atoms.
33. The method of claim 32 in which the alcohol is selected from the group consisting of methanol, butanol and mixtures thereof.
34. The method of claim 32 in which the aminoplast crosslinking agent is fully alkylated.
35. The method of claim 19 in which the clear film-forming composition has a hydroxyl value of less than 70 based on total weight of resin solids in the clear film-forming composition.
36. A method for applying a composite coating to a substrate that comprises:
(a) applying to the substrate a colored film-forming composition to form a base coat and (b) applying to said base coat a clear film-forming composition to form a transparent top coat over the base coat wherein the clear film-forming composition comprises:
(i) 40 to 60 percent by weight of a polymer or oligomer containing repeating ester groups in the polymer or oligomer backbone and containing a plurality of terminal carbamate groups of the structure:
(ii) 40 to 60 percent by weight of a hydroxyl functional acrylic copolymer; and (iii) 25 to 50 percent by weight of a fully alkylated aminoplast crosslinking agent;
the percentages by weight of (i) and (ii) being based on total resin solids weight of (i) plus (ii); the percentage by weight of (iii) being based on total weight of resin solids in the clear film-forming composition.
(a) applying to the substrate a colored film-forming composition to form a base coat and (b) applying to said base coat a clear film-forming composition to form a transparent top coat over the base coat wherein the clear film-forming composition comprises:
(i) 40 to 60 percent by weight of a polymer or oligomer containing repeating ester groups in the polymer or oligomer backbone and containing a plurality of terminal carbamate groups of the structure:
(ii) 40 to 60 percent by weight of a hydroxyl functional acrylic copolymer; and (iii) 25 to 50 percent by weight of a fully alkylated aminoplast crosslinking agent;
the percentages by weight of (i) and (ii) being based on total resin solids weight of (i) plus (ii); the percentage by weight of (iii) being based on total weight of resin solids in the clear film-forming composition.
37. The coated article prepared by the method of claim 19.
38. The coated article prepared by the method of claim 20.
39. The coated article prepared by the method of claim 36.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/562,234 | 1995-11-21 | ||
| US08/562,234 US5593733A (en) | 1995-11-21 | 1995-11-21 | Coating composition containing polyester polymers with terminal carbamate groups and polymeric polyol derived from ethylenically unsaturated monomers |
| PCT/US1996/018701 WO1997019139A1 (en) | 1995-11-21 | 1996-11-18 | Coating composition containing polyester polymers with terminal carbamate groups and polymeric polyol derived from ethylenically unsaturated monomers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2231539A1 CA2231539A1 (en) | 1997-05-29 |
| CA2231539C true CA2231539C (en) | 2002-02-05 |
Family
ID=24245393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002231539A Expired - Lifetime CA2231539C (en) | 1995-11-21 | 1996-11-18 | Coating composition containing polyester polymers with terminal carbamate groups and polymeric polyol derived from ethylenically unsaturated monomers |
Country Status (10)
| Country | Link |
|---|---|
| US (2) | US5593733A (en) |
| EP (1) | EP0862601B1 (en) |
| JP (1) | JP3276153B2 (en) |
| BR (1) | BR9611591A (en) |
| CA (1) | CA2231539C (en) |
| DE (1) | DE69606198T2 (en) |
| ES (1) | ES2144274T3 (en) |
| MX (1) | MX9803626A (en) |
| PT (1) | PT862601E (en) |
| WO (1) | WO1997019139A1 (en) |
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| MX253908B (en) * | 1999-07-30 | 2008-01-28 | Ppg Ind Ohio Inc | Coating compositions having improved scratch resistance, coated substrates and methods related thereto. |
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| WO2001009260A1 (en) * | 1999-07-30 | 2001-02-08 | Ppg Industries Ohio, Inc. | Coating compositions having improved scratch resistance, coated substrates and methods related thereto |
| WO2001009231A1 (en) | 1999-07-30 | 2001-02-08 | Ppg Industries Ohio, Inc. | Cured coatings having improved scratch resistance, coated substrates and methods related thereto |
| US6623791B2 (en) | 1999-07-30 | 2003-09-23 | Ppg Industries Ohio, Inc. | Coating compositions having improved adhesion, coated substrates and methods related thereto |
| US6228953B1 (en) * | 1999-08-20 | 2001-05-08 | Ppg Industries,Ohio, Inc. | Process for the preparation of carbamate functional polymers |
| US6362285B1 (en) | 1999-12-15 | 2002-03-26 | Basf Corporation | Curable coating compositions containing carbamate functional reactive additives |
| US6391968B1 (en) | 1999-12-15 | 2002-05-21 | Basf Corporation | Curable coating compositions containing carbamate functional polymers and carbamate functional reactive additives |
| US6303690B1 (en) | 1999-12-15 | 2001-10-16 | Basf Corporation | Cathodic electrocoat having a carbamate functional resin and a carbamate functional reactive additive |
| US6380323B1 (en) | 1999-12-15 | 2002-04-30 | Basf Corporation | Electrocoat resin compositions containing carbamate functional resins having one or more quaternary ammonium groups and at least one carbamate functional reactive additive |
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| US6635341B1 (en) * | 2000-07-31 | 2003-10-21 | Ppg Industries Ohio, Inc. | Coating compositions comprising silyl blocked components, coating, coated substrates and methods related thereto |
| DE10041634C2 (en) * | 2000-08-24 | 2002-10-17 | Basf Coatings Ag | Aqueous dispersion and its use for the production of coating materials, adhesives and sealants curable thermally and with actinic radiation |
| US6657007B2 (en) * | 2000-09-29 | 2003-12-02 | Basf Corporation | Clearcoat composition with improved adhesion |
| US6544596B2 (en) | 2000-11-29 | 2003-04-08 | Pacific Northwest Coatings | Method of coating a substrate using a thermosetting basecoat composition and a thermoplastic top coat composition |
| US6541577B2 (en) * | 2000-12-06 | 2003-04-01 | Basf Corporation | Carbamate functional polymers and oligomers |
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| US20050228124A1 (en) * | 2002-04-19 | 2005-10-13 | Shanti Swarup | Coating compositions containing highly crosslinked polymer particles and a hydrophobic polymer |
| US6716953B2 (en) | 2002-05-16 | 2004-04-06 | Ppg Industries Ohio, Inc. | Etherified carbamate crosslinking agents and their use in curable compositions, particularly film-forming compositions |
| US7144966B2 (en) * | 2004-03-04 | 2006-12-05 | Basf Corporation | Acrylic composition for use in coating applications and a method of forming the same |
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| US7807743B2 (en) * | 2006-09-22 | 2010-10-05 | Basf Corporation | Coating composition and film system therefrom |
| CN101578327B (en) * | 2007-02-13 | 2011-12-21 | 尤尼吉可株式会社 | Highly adhesive film |
| US20110021694A1 (en) * | 2009-07-23 | 2011-01-27 | E.I. Du Pont De Nemours And Company | Polyesterurethane for coating compositions |
| US20150337143A1 (en) | 2012-06-22 | 2015-11-26 | Ppg Coatings Europe B.V. | Antifouling Coating Composition |
| US20140255608A1 (en) | 2013-03-11 | 2014-09-11 | Ppg Industries Ohio, Inc. | Coatings that exhibit a tri-coat appearance, related coating methods and substrates |
| EP3134451B1 (en) * | 2013-09-17 | 2018-11-28 | Dow Global Technologies LLC | A method for producing polycarbamate, a polycarbamate produced thereby and a coating containing the polycarbamate |
| US20150197667A1 (en) | 2014-01-15 | 2015-07-16 | Ppg Industries Ohio, Inc. | Polyester polymers comprising lignin |
| EP3399002B1 (en) * | 2015-12-28 | 2020-08-26 | KCC Corporation | Highly scratch resistant one-pack type paint composition |
| US10767073B2 (en) * | 2016-10-18 | 2020-09-08 | Ppg Industries Ohio, Inc. | Curable film-forming compositions containing hydroxyl functional, branched acrylic polymers and multilayer composite coatings |
| CA3192128A1 (en) | 2020-10-05 | 2022-04-14 | Jacob W. MOHIN | High transfer efficiency application methods and shear thinning coating compositions for application using the methods |
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| US3464938A (en) * | 1966-11-18 | 1969-09-02 | Ashland Oil Inc | Modified carbamate ester containing polymers |
| US4374164A (en) * | 1981-12-14 | 1983-02-15 | American Cyanamid Company | High solids polymer resin coating composition containing amino resin cross-linking agent |
| EP0257848A3 (en) * | 1986-08-14 | 1989-01-11 | King Industries, Inc. | Certain carbamates, processes for preparing same and use thereof |
| US5169725A (en) * | 1991-08-29 | 1992-12-08 | Morton International, Inc. | Utilization of flexible coating on steel to impart superior scratch and chip resistance |
| US5356669A (en) * | 1992-10-23 | 1994-10-18 | Basf Corporation | Composite color-plus-clear coating utilizing carbamate-functional polymer composition in the clearcoat |
| ZA937635B (en) * | 1992-10-23 | 1994-05-05 | Basf Corp | Curable carbamate-functional polymer composition |
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| US6103816A (en) * | 1992-10-30 | 2000-08-15 | Ppg Industries Ohio, Inc. | Aqueous aminoplast curable film-forming compositions providing films having resistance to acid etching |
| US5336566A (en) * | 1993-04-30 | 1994-08-09 | Basf Corporation | Tri-carbamate-functional crosslinking agents |
| US5744550A (en) * | 1994-11-03 | 1998-04-28 | Basf Corporation | Curable coating compositions containing carbamate additives |
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| US6165618A (en) * | 1994-11-03 | 2000-12-26 | Basf Corporation | Curable coating compositions containing carbamate resin and additives |
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| US5412049A (en) * | 1994-03-31 | 1995-05-02 | Union Carbide Chemicals & Plastics Technology Corporation | Polymer compositions containing hydroxyl functional (meth)acrylates and hydroxyalkyl carbamate (meth)acrylates and mixtures thereof |
| US5451656A (en) * | 1994-12-21 | 1995-09-19 | Basf Corporation | Carbamate-functional polyester polymer or oligomer and coating composition |
-
1995
- 1995-11-21 US US08/562,234 patent/US5593733A/en not_active Expired - Lifetime
-
1996
- 1996-08-23 US US08/702,376 patent/US5646214A/en not_active Expired - Lifetime
- 1996-11-18 DE DE69606198T patent/DE69606198T2/en not_active Expired - Lifetime
- 1996-11-18 JP JP51990197A patent/JP3276153B2/en not_active Expired - Fee Related
- 1996-11-18 EP EP96940841A patent/EP0862601B1/en not_active Expired - Lifetime
- 1996-11-18 BR BR9611591A patent/BR9611591A/en not_active IP Right Cessation
- 1996-11-18 ES ES96940841T patent/ES2144274T3/en not_active Expired - Lifetime
- 1996-11-18 WO PCT/US1996/018701 patent/WO1997019139A1/en active IP Right Grant
- 1996-11-18 CA CA002231539A patent/CA2231539C/en not_active Expired - Lifetime
- 1996-11-18 PT PT96940841T patent/PT862601E/en unknown
-
1998
- 1998-05-07 MX MX9803626A patent/MX9803626A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0862601B1 (en) | 2000-01-12 |
| EP0862601A1 (en) | 1998-09-09 |
| DE69606198D1 (en) | 2000-02-17 |
| DE69606198T2 (en) | 2000-07-13 |
| CA2231539A1 (en) | 1997-05-29 |
| JPH11500488A (en) | 1999-01-12 |
| US5646214A (en) | 1997-07-08 |
| JP3276153B2 (en) | 2002-04-22 |
| BR9611591A (en) | 1999-04-06 |
| ES2144274T3 (en) | 2000-06-01 |
| MX9803626A (en) | 1998-09-30 |
| PT862601E (en) | 2000-04-28 |
| WO1997019139A1 (en) | 1997-05-29 |
| US5593733A (en) | 1997-01-14 |
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