EP1356001A2 - Composition de revetement a base d'eau, presentant une reticulation de carbamate-melamine, procede de fabrication correspondant et film durci issu de cette composition - Google Patents

Composition de revetement a base d'eau, presentant une reticulation de carbamate-melamine, procede de fabrication correspondant et film durci issu de cette composition

Info

Publication number
EP1356001A2
EP1356001A2 EP01990645A EP01990645A EP1356001A2 EP 1356001 A2 EP1356001 A2 EP 1356001A2 EP 01990645 A EP01990645 A EP 01990645A EP 01990645 A EP01990645 A EP 01990645A EP 1356001 A2 EP1356001 A2 EP 1356001A2
Authority
EP
European Patent Office
Prior art keywords
coating composition
water
set forth
functional group
block
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01990645A
Other languages
German (de)
English (en)
Inventor
Swaminathan Ramesh
Paul Lessek
Wolfgang Bremser
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Corp
Original Assignee
BASF Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/747,473 external-priority patent/US6699943B2/en
Application filed by BASF Corp filed Critical BASF Corp
Publication of EP1356001A2 publication Critical patent/EP1356001A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups

Definitions

  • the subject invention generally relates to a curable, water-based coating
  • composition utilized primarily in waterborne coating systems such as waterborne
  • WBBC basecoat
  • WBCC waterborne clearcoat
  • the coating composition includes a water-based
  • copolymer having a carbamate functional group, and a cross-linking agent that is
  • invention also relates to a method of preparing the coating composition as well as a
  • Water-based coating compositions include water-based copolymers and
  • cross-linking agents as components.
  • the water-based copolymers are desirable for
  • waterborne coating systems are ideal as compared to solventborne coating systems
  • the water-based coating compositions for use as a component in water-based coating compositions.
  • the water-based coating compositions for use as a component in water-based coating compositions.
  • copolymers often incorporate additional components such as co-solvents and
  • characteristics of the WBBC, WBCC, or waterborne primer system such as gloss
  • DOI distinctness of image
  • water-based coating composition as detailed above, are characterized by one or
  • a curable, water-based coating composition is disclosed.
  • coating composition of the subject invention is the reaction product of a water-
  • the water-based copolymer (A) is prepared by free-radical polymerization and
  • first block polymer or first block, (A)(1) and a second block (A)(H).
  • the first block (A)(1) is preferably a hydrophilic block, and the second block
  • (A)(IT) is preferably a hydrophobic block. More specifically, the first block (A)(1)
  • the reaction product of the copolymer (A) is the reaction product of at least one ethylenically
  • the second block (A)(H) of the copolymer (A) is the reaction
  • plurality includes at least one carbonate functional group for modification into a
  • the cross-linking agent (B) is reactive with the
  • the first ethylenically unsaturated monomer is preferably acrylic acid
  • the second ethylenically unsaturated monomer is preferably methyl methacrylate.
  • first block (A)(1) is preferably diphenylethylene. Also in the preferred embodiment
  • monomer (A)(1)(a) are styrene, 2-ethylhexyl methacrylate, cyclohexyl methacrylate,
  • the carbamate functional group is hexamethoxymethyl melamine.
  • the first block (A)(1) is first formed.
  • the second block (A)(II), having the at least one carbonate functional group is
  • the at least one carbonate functional group is then converted into at least one
  • copolymer (A) is then combined with the water-
  • the general object of the subject invention is to develop a water-based
  • coating composition for use in WBBC, WBCC, and waterborne primer systems
  • the carbamate functional group such that the WBBC, WBCC, and waterborne
  • the curable, water-based coating composition of the subject invention is
  • Waterborne coating systems such as
  • WBBC waterborne basecoat
  • WBCC waterborne clearcoat
  • the water-based coating composition of the subject invention includes the
  • the water-based coating composition is prepared by:
  • coating composition includes the steps of forming a first block (A)(1), polymerizing
  • copolymer (A) converting a carbonate functional group of the copolymer (A) into
  • the water-based copolymer (A) is the reaction product of the first block
  • block (A)(1) is a hydrophilic block
  • the second block (A)(II) is a hydrophobic
  • water-based copolymer (A) could also be
  • hydrophilic block and a first hydrophobic block.
  • the first block (A)(1) is present in an amount from 5 to 15, preferably from
  • the first block (A)(1) is the reaction product of at least one ethylenically
  • hydrocarbon monomer (A)(1)(b) are polymerized. This polymerization step is
  • step be conducted under pressure. If required, such pressure is preferably from 1.5
  • the at least one ethylenically unsaturated monomer (A)(1)(a) of the first block (A)(1) is selected primarily to ensure the solubility of the copolymer (A) in
  • the at least one ethylenically unsaturated monomer (A)(1)(a) is
  • the neutralizing is selected to form a salt when reacted with a neutralizing agent.
  • unsaturated monomer (A)(1)(a) may also be selected to achieve an ideal minimum
  • the WBBC, WBCC, or waterborne primer system such that the cured film is
  • ethylenically unsaturated monomer (A)(1)(a) may also be selected to minimize the
  • ethylenically unsaturated monomer (A)(1)(a) is further defined as a first and second
  • copolymer (A) the first and second ethylenically unsaturated monomers form from
  • the total monomer composition in the first block (A)(1) also includes the content of
  • vinylaromatic hydrocarbon monomer (A)(1)(b) is alternatively defined as at least
  • the total monomer composition in the first block (A)(1) is
  • second ethylenically unsaturated monomer in the first block (A)(1) is from 1 : 0.5 to
  • the first ethylenically unsaturated monomer is selected from the group of
  • monomer is selected from the group of compounds consisting of aliphatic
  • each of these compounds includes
  • alkyl acrylic acids that may be selected as the first ethylenically unsaturated monomer are selected from the group consisting of acrylic acid,
  • methacrylic acid ethacrylic acid
  • maleic acid fumaric acid
  • itaconic acid crotonic
  • the aliphatic acrylates that may be selected as the
  • second ethylenically unsaturated monomer are selected from the group consisting of
  • aliphatic methacrylates that may be selected as the second ethylenically unsaturated
  • monomer are selected from the group consisting of methyl methacrylate, ethyl
  • cycloaliphatic acrylate that may be selected as the second
  • ethylenically unsaturated monomer is cyclohexyl acrylate, and the cycloaliphatic
  • methacrylate that may be selected as the second ethylenically unsaturated monomer
  • ethylenically unsaturated monomer is acrylic acid, and the second ethylenically unsaturated monomer
  • unsaturated monomer is methyl methacrylate. Furthermore, the weight ratio of the unsaturated monomer
  • acrylic acid to the methyl methacrylate in the first block (A)(1) is from 1 : 0.5 to 1 :
  • block (A)(1) is selected from the group consisting of ⁇ -methylstyrene,
  • diphenylethylene diphenylethylene, dinapthaleneethylene, and mixtures thereof. Further, it is to be
  • ⁇ -alkylstyrenes may be selected as the at least one vinylaromatic hydrocarbon monomer (A)(1)(b) as well as other equivalent
  • subject invention includes only one vinylaromatic hydrocarbon monomer, most
  • the at least one vinylaromatic hydrocarbon is selected from the at least one vinylaromatic hydrocarbon
  • radicals R ⁇ , R , R , and R ⁇ each independently of
  • one another are hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl,
  • alkylcycloalkyl cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or
  • R , and Rj are substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals
  • aryl radicals especially substituted or unsubstituted aryl radicals.
  • suitable alkyl radicals are methyl, ethyl, propyl, isopropyl,
  • n-butyl isobutyl, tert-butyl, amyl, hexyl, or 2-ethylhexyl.
  • Suitable cycloalkyl radicals are cyclobutyl, cyclopentyl, or
  • alkylcycloalkyl radicals examples include methylenecyclohexane,
  • Suitable cycloalkylalkyl radicals are 2-, 3-, or 4-methyl-, -ethyl-, -propyl-, or -butylcyclohex -1-yl.
  • Suitable aryl radicals are phenyl, naphthyl or biphenylyl,
  • phenyl and naphthyl preferably phenyl and naphthyl, and especially phenyl.
  • alkylaryl radicals examples include benzyl or ethylene- or
  • Suitable cycloalkylaryl radicals are 2-, 3-, or
  • arylalkyl radicals 2-, 3-, or 4-methyl-, -ethyl-,
  • Suitable arylcycloalkyl radicals are 2-, 3-, or
  • substituents used may comprise electron-withdrawing or electron-donating atoms
  • halogenated especially chlorinated and/or fluorinated, alkyl, cycloalkyl,
  • aryloxy, alkyloxy and cycloalkyloxy radicals especially phenoxy, naphthoxy,
  • arylthio, alkylthio and cycloalkylthio radicals especially phenylthio, naphthylthio, methylthio, ethylthio,
  • N,N,-dicyclohexylamino N-cyclo-hexyl-N-methylamino and N-ethyl-N-methylamino.
  • monomers (A)(1)(b) may be used individually or as a mixture of at least two
  • unsaturated monomers (A)(1)(b) in these alternative embodiments is diphenylethylene.
  • the first block In addition to the at least one ethylenically unsaturated monomer (A)(1)(a) and the at least one vinylaromatic hydrocarbon monomer (A)(1)(b), the first block
  • (A)(1) is also the reaction product of the neutralizing agent. That is, the
  • neutralizing agent is selected from the group consisting of dimethylethanolamine,
  • base neutralizing agents may selected including, but not limited to, sodium
  • hydroxide potassium hydroxide, diethanolamine, triethanolamine, and mono-, di-,
  • the neutralizing agent is ammonia
  • the ammonia, NH 3 interacts with an acid group of the first ethylenically
  • ammonia NH 3
  • NH 3 interacts with the hydrogen atom of the -COOH group of the
  • acrylic acid to form a salt of the acrylic acid, having a -COO " group, i.e., an acid
  • an initiator also known a polymerization
  • the initiator initiates the free-
  • the initiator is soluble in water and is selected
  • the initiator is an inorganic persulfate selected from the
  • the initiator is sodium persulfate, Na S 2 O 8 .
  • the initiator is sodium persulfate
  • polymerization initiator may be a dialkyl peroxides such as di-tert-butyl peroxide
  • hydroperoxide such as cumene hydroperoxide or tert-butyl
  • hydroperoxide or a perester, such as tert-butyl perbenzoate, tert-butyl perpivalate,
  • the weight ratio of the initiator to the at least one vinylaromatic radical is the weight ratio of the initiator to the at least one vinylaromatic radical
  • hydrocarbon monomer (A)(1)(b) is preferably from 1 : 3 to 3 : 1. It is to be
  • the initiator be present in an amount from 0.5
  • block (A)(1) has a non- olatile content of from 20 to 40, preferably from 25 to 35,
  • the completed first block (A)(1) has a
  • M n number average molecular weight, from 1,000 to 20,000, preferably from
  • this polymerization step is preferably initiated by self-formation of
  • hydrocarbon monomer (A)(1)(b) of the first block (A)(1) in the preferred
  • diphenylethylene controls the polymerization of the incoming
  • copolymer (A) is more specifically the reaction product of a plurality of
  • the plurality of ethylenically unsaturated monomers (A)(II)(a) are
  • the plurality of ethylenically unsaturated monomers (A)(IT)(a) are also present.
  • (A)(II)(a) includes at least one carbonate functional group. As such, the plurality of
  • ethylenically unsaturated monomers (A)(H)(a) are selected from the group
  • the carbonate functional group can then be converted
  • glycidyl acrylate is formed by the reaction of glycidyl acrylate, having the chemical
  • ethylenically unsaturated monomers (A)(IT)(a) that are selected are styrene, 2-
  • methacrylate which includes the carbonate functional group.
  • methacrylate is 4-(hydroxymethyl)-l,3-dioxolan-2-one methacrylate and the
  • second block (A)(IT) of the copolymer (A) is then modified, i.e., converted, into the
  • ammonia-containing compound is selected from the group consisting of
  • the second block (A)(II) is polymerized with the first block (A)(1), it is to be
  • ammonium hydroxide is utilized to convert
  • group of the ammonium hydroxide can form a primary carbamate functional
  • ammonia, NH , group of the ammonium hydroxide can form a
  • the water-based coating composition is also the reaction product of the at
  • the water-based copolymer (A) is a water-based copolymer (A)
  • sulfonate-based surfactant is selected as the anionic surfactant.
  • the cross-linking agent (B) is selected from the group consisting of water-
  • cross-linking agent (B) is present in an amount from .1 to 10, preferably from .05 to 5, and most preferably from 1 to 3, parts by weight based on 100 parts by weight of the coating composition.
  • water-dispersible aminoplasts include urea
  • the preferred embodiment include either a methylol group, CH OH, an
  • alkoxymethyl group or both.
  • the alkoxymethyl group is of the general formula —
  • R 1 is an alkyl chain having from 1 to 20 carbon atoms.
  • cross-linking agents include, but are not limited to, monomeric and
  • polymeric melamine formaldehyde resins including both partially and fully
  • alkylated melamines such as methylated melamines, butylated melamines, and
  • cross-linking agents (B) that are urea
  • resins include methylol ureas such as urea formaldehyde resins, and alkoxy ureas
  • HMMM hexamethoxymethyl melamine
  • the alkoxymethyl groups of the HMMM reacts with the carbamate functional group in the second block (A)QI) of the copolymer (A) to establish a urethane ( — NH — CO — O — ) linkage without use of an isocyanate.
  • the urethane linkage between the copolymer (A) and the cross-linking agent (B) is from the carbamate - melamine reaction and is ideal for resistance to environmental acid etch.
  • the copolymer (A) has a number-average molecular weight, M n , of from 5,000 to 2,000,000.
  • the coating composition of the subject invention has a non-volatile content of from 20 to 60, preferably from 30 to 50,
  • the cured film of the water-based coating composition of the subject invention is prepared by applying the water-based coating composition to the substrate. More specifically, the water-based coating composition can be sprayed onto the substrate by air-atomized or bell-applied spray application, and other equivalent processes. Once applied to the substrate, the coating composition is cured to form the cured film. Although cross-linking may occur prior to the curing step, the cross-linking agent (B) completely reacts with the at least one carbamate functional group during the curing step to form the cured film of the water-based coating composition including the urethane cross-linking.
  • the reaction between the cross-linking agent (B) and the carbamate functional group occurs at a temperature between 100°C and 175°C, and more preferably at a temperature between 110°C and 130°C from 20 to 30 minutes. It is to be understood that all of the preceding chemical representations are
  • the first block (A)(1) of the copolymer (A) was prepared by adding and
  • reaction flask preferably a steel reactor
  • the first feed stream included 203.6 grams of
  • the second feed stream included 198.3 grams of the
  • polymerization step included the following parts, by weight, unless otherwise
  • reaction flask The reaction flask, including the water, was heated via a conventional heat supply to a temperature of 90°C for approximately 30 minutes.
  • the second block (A)(II) feed stream included 157.9 grams of
  • Example 3 In Example 3, the carbonate functional group of the initial form of
  • copolymer (A) was converted into the carbamate functional group according to the
  • reaction flask The reaction flask, including the water, was heated via a
  • ammonium hydroxide were added into the reaction flask over approximately 1 to 2
  • ammomum hydroxide were added into the reaction flask at 60°C over
  • the MEK double rub method is an acceptable method for initial
  • Example 4 the completed copolymer (A) and the cross-linking agent (B)
  • composition as depicted in this example is merely a preliminary 'scale-up'
  • primer systems that may include other components such as pigments, flow
  • composition was prepared according to the following parts, by weight, unless
  • HMMM hexamethoxymethyl melamine
  • the copolymer (A) was first added into a container, and then the
  • cross-linking agent (B) was added into the container, including the copolymer (A),
  • anionic surfactant specifically 1.0
  • Sample A was spray applied to a substrate, specifically ACT
  • Sample A was
  • coating composition was evaluated for appearance and initial physical property
  • the general appearance of the cured film was uniform and acceptable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention porte sur une composition de revêtement à base d'eau, durcissante, utilisée dans les systèmes de revêtement à l'eau. Cette composition est le produit de réaction d'un copolymère à base d'eau obtenu au cours d'une polymérisation par radical libre et d'un agent de réticulation. Le copolymère est le produit de réaction d'un premier bloc et d'un second bloc. Le premier bloc est non seulement le produit de réaction d'un premier monomère éthylétiquement insaturé, l'acide acrylique et d'un second monomère éthylétiquement insaturé, le méthacrylate de méthyle, mais aussi le produit de réaction d'un monomère d'hydrocarbure vinylaromatique, le diphényléthylène. Le deuxième bloc est le produit de réaction de plusieurs monomères éthylétiquement insaturés, le styrène, le 2-ethylexyl méthacrylate, le méthacrylate cyclohexyle, et le méthacrylate glycidyle à modification par carbonate contenant un groupe fonctionnel de carbonate qui sera par la suite transformé en groupe fonctionnel de carbamate au moyen d'hydroxyde d'ammonium. L'agent de réticulation, de préférence une mélamine, réagit avec le groupe fonctionnel de carbamate afin de produire une composition de revêtement présentant une réticulation d'uréthane issue de la réaction de carbamate-mélamine.
EP01990645A 2000-12-22 2001-11-19 Composition de revetement a base d'eau, presentant une reticulation de carbamate-melamine, procede de fabrication correspondant et film durci issu de cette composition Withdrawn EP1356001A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US09/747,473 US6699943B2 (en) 2000-06-16 2000-12-22 Water-based coating composition having carbamate-melamine cross-linking, method of preparing the same, and a cured film thereof
US747473 2000-12-22
PCT/US2001/042953 WO2002051952A2 (fr) 2000-12-22 2001-11-19 Composition de revetement a base d'eau, presentant une reticulation de carbamate-melamine, procede de fabrication correspondant et film durci issu de cette composition

Publications (1)

Publication Number Publication Date
EP1356001A2 true EP1356001A2 (fr) 2003-10-29

Family

ID=25005201

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01990645A Withdrawn EP1356001A2 (fr) 2000-12-22 2001-11-19 Composition de revetement a base d'eau, presentant une reticulation de carbamate-melamine, procede de fabrication correspondant et film durci issu de cette composition

Country Status (6)

Country Link
EP (1) EP1356001A2 (fr)
AU (1) AU2002230412A1 (fr)
BR (1) BR0114923A (fr)
CA (1) CA2425948A1 (fr)
MX (1) MXPA03003210A (fr)
WO (1) WO2002051952A2 (fr)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5726244A (en) * 1995-08-10 1998-03-10 Basf Corporation Aqueous coating compositions for environmental etch resistant coatings
US6120120A (en) * 1997-08-19 2000-09-19 Brother Kogyo Kabushiki Kaisha Ink jet apparatus and ink jet recorder

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO02051952A2 *

Also Published As

Publication number Publication date
CA2425948A1 (fr) 2002-07-04
WO2002051952A2 (fr) 2002-07-04
BR0114923A (pt) 2003-12-23
AU2002230412A1 (en) 2002-07-08
MXPA03003210A (es) 2003-06-24
WO2002051952A3 (fr) 2003-02-20

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