WO2004104121A1 - Systemes de revetement reticulables contenant des esters de carboxyalkylcellulose - Google Patents

Systemes de revetement reticulables contenant des esters de carboxyalkylcellulose Download PDF

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Publication number
WO2004104121A1
WO2004104121A1 PCT/US2004/013983 US2004013983W WO2004104121A1 WO 2004104121 A1 WO2004104121 A1 WO 2004104121A1 US 2004013983 W US2004013983 W US 2004013983W WO 2004104121 A1 WO2004104121 A1 WO 2004104121A1
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WO
WIPO (PCT)
Prior art keywords
crosslinker
alkyd
resistance
resins
print
Prior art date
Application number
PCT/US2004/013983
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English (en)
Inventor
Ronald Todd Obie
Original Assignee
Eastman Chemical Company
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
Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Publication of WO2004104121A1 publication Critical patent/WO2004104121A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/32—Cellulose ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/32—Cellulose ether-esters
    • 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
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine

Definitions

  • the invention relates to crosslinking compositions, and more specifically, to crosslinking coating compositions containing carboxyalkyl cellulose esters.
  • the inventive coating compositions exhibit improved cure properties over comparable crosslinking compositions lacking such esters.
  • Aminoplast and phenolplast resins are the two most common types of crosslinking resins, and can be used to crosslink coating compositions containing a variety of polymer resins or binders. This crosslinking results in improved coating cure speed, and in improved physical properties in the coating compared to coating compositions that cure via physical drying, or via thermoplastic or oxidative curing.
  • Aminoplast and phenolplast crosslinkers essentially function by reaction of functional groups on the crosslinker with functional groups of the polymer resin.
  • Examples of polymer resins that can be cured via crosslinking include alkyd, polyester, epoxy, acrylic, and siloxane resins. Reactive functionalities of these polymer resins include hydroxyl, carboxyl, epoxy, and amine functionalities.
  • Phenolplast or phenolic crosslinking resins are typically made by reacting phenols with formaldehyde, through a condensation reaction, to yield a phenol-formaldehyde resin, though aldehydes other than formaldehyde may also be used. Phenol-formaldehyde resins thus consist of aromatic rings linked by methylene or oxymethylene groups. Thermosetting phenol- formaldehyde resins are typically used to develop container coatings, and may be blended with the backbone resins already described. Aminoplast or amino-formaldehyde crosslinking agents are made by reacting formaldehyde with an amine through a condensation reaction, followed by alkylation of the resulting methylol groups with an alcohol.
  • the chemical and physical properties of the aminoplast resin or crosslinker are determined by the choice of amine used in the condensation reaction, the molar ratio of amine to formaldehyde, the choice of alkylation alcohol, and the degree of alkylation of the methylol groups formed during the condensation reaction.
  • Aminoplast crosslinkers are used in both solvent-based and water-based systems.
  • Improved cure speeds are important for increased article processing speeds and lower energy requirements.
  • Urea- formaldehyde resins are typically used in coatings when faster cure speeds are desired.
  • Melamine-formaldehyde resins are used when improved water, detergent, and overall physical properties are desired, and are not obtained with urea-formaldehyde resins.
  • melamine-formaldehyde resins are typically slower in cure speed than are urea formaldehyde resins.
  • Melamine-formaldehyde crosslinkers are therefore often selected because of their improved performance and pot/shelf life as compared to urea formaldehyde-crosslinkers. However, this can mean a compromise between cure speed and performance, due to the slower cure speeds of the melamine formaldehyde resins.
  • Resimene 797 available from Monsanto/Solutia
  • Resimene 2040 also available from Monsanto/Solutia
  • Modacure another product of Monsanto/Solutia, is a hexamethoxymethylmelamine-based crosslinker modified with up to 60% styrene allyl alcohol, based on total crosslinker solids.
  • the styrene allyl alcohol in these products is used to modify melamine in such a way as to produce a faster curing melamine.
  • These resins thus show improved cure response compared to the typical commercially available melamine-formaldehyde resins.
  • WO 01/60882 describes alkoxymethyl melamine crosslinkers, having reduced levels of imino groups, that yield improved cure response.
  • Resimene CE-7103 a product that yields improved cure response for melamine-formaldehyde resins.
  • Resimene CE-7103 is a highly etherified, low molecular weight, co-etherified melamine-formaldehyde resin. It is said to provide crosslinked coating systems requiring lower temperature cure, reduced catalyst requirements, lower evolved formaldehyde, improved flexibility, lower free formaldehyde, and lower viscosity and VOC.
  • Cytec has introduced Cymel 104 and 105 to address improved cure response in MF resins.
  • Cymel 104 resin is an 80/20 solids blend of Cymel 303 resin (a highly methylolated, highly methylated melamine resin) with REACTOL 180 polyol (a hydroxyl-functional resin supplied by Eastman Chemical Co., Kingsport, TN); Cymel 105 resin is a 60/40 solids blend of Cymel 303 and REACTOL 180. These products are claimed to show , improved cure response, higher film hardness, and improved corrosion resistance relative to 100% Cymel 303 resin.
  • the invention provides a crosslinking coating composition, containing an aminoplast crosslinker, and having improved cure speed over traditional aminoplast crosslinkers, as measured by mar resistance, block resistance, and print resistance tests.
  • carboxyalkyl cellulose esters relatively hydrophobic polymers containing both acid groups and hydroxyl groups, are dissolved in a solvent and subsequently blended with an aminoplast crosslinker.
  • carboxy- methylcellulose acetate butyrate is dissolved in methanol or ethanol and subsequently blended with a liquid hexamethoxymethylmelamine. This mixture may be used as is; added to a mixture containing an alkyd resin; or added to a mixture containing any other compatible polymer composition.
  • the finished mixture can then be catalyzed with PTSA or any other catalyst material.
  • PTSA any other catalyst material.
  • the mixture of carboxymethylcellulose acetate butyrate and a liquid hexamethoxymethylmelamine provides dramatically improved cure response and print and block resistance over a crosslinker containing an acrylic polyol or Styrene Allyl Alcohol. At the same time, the mixture provides improved flow and leveling.
  • the present invention provides an aminoplast crosslinker having improved cure speed, as measured by mar resistance, block resistance, and print resistance test results.
  • carboxyalkyl cellulose esters relatively hydrophobic polymers containing both acid groups and hydroxyl groups, are dissolved in a solvent, and subsequently blended with a crosslinker, and especially an aminoplast crosslinker.
  • carboxymethylcellulose acetate butyrate is dissolved in methanol or ethanol and subsequently blended with a liquid hexamethoxymethylmelamine to obtain a crosslinker system blend.
  • This blend may be used as such; added to a mixture containing an alkyd resin; or added to a mixture containing any other compatible polymer.
  • the final mixture may then be catalyzed with PTSA, or with any other suitable catalyst material.
  • the blends provide dramatically improved cure response and print and block resistance over a crosslinker containing an acrylic polyol or styrene allyl alcohol as the polyol.
  • the carboxymethylcellulose acetate butyrate /liquid hexamethoxymethylmelamine blend provides improved flow and leveling.
  • Other amino and phenolplast resins are also useful according to the invention, such as Tris alkoxy carbonyl triazine type products, for example.
  • the carboxymethylcellulose acetate butyrate-modified hexamethoxymethylmelamine solution of example 1 was added to a coating based on a short oil alkyd resin (Duramac 207-1205, available from Eastman Chemical Co., Kingsport, TN), and the results compared to the cure and appearance of Resimene 2040, a 40% styrene allyl alcohol- modified hexamethoxymethylmelamine crosslinker available from Solutia.
  • a short oil alkyd resin (Duramac 207-1205, available from Eastman Chemical Co., Kingsport, TN)
  • Print resistance was checked by performing 6 mil draw downs on plate glass. The draw downs air-dried for 15 minutes, cured for 10 minutes @ 66C, and cooled for 5 minutes. A 2 psi and 4 psi print test was applied for 2 hours. Clarity, mar resistance, and flow and leveling were evaluated by 1.5 mil draw downs and 6 mil draw downs on Leneta Form 7B. These draw downs cured on the same schedule as those on the plate glass. The results are detailed below in Table 4.
  • Example 1 carboxymethylcellulose acetate butyrate/Melamine blend results in better print/block and mar resistance and better overall hardness than Resimene 2040.
  • the Example 1 modified coating results in a more hazy appearance on plate glass however.
  • Examples 8 - 21 detail studies evaluating compatibility of the carboxymethylcellulose acetate butyrate /Melamine blend of Example 1 with various alkyd resins.
  • Alkyd resins are often used as backbone resins in aminoplast based coatings. Alkyd resins are the reaction product of a dibasic acid such as phthalic acid with an alcohol such as glycerol.
  • alkyd resins are the reaction products of a dibasic acid such as phthalic acid, a polyol such as glycerol: and a fatty acid such as linseed oil. (There are other modifications that may be made as well.)
  • the amount of defunctionalization i.e., the amount of fatty acid used, provides a third classification of the alkyd, i.e., oil length.
  • short oil alkyds are those that contain ⁇ 40% oil
  • medium oil alkyds are those that contain oil contents of 40 - 50% while long oil alkyds contain >55% oil.
  • Akzo 21-1106 is a short oil coconut alkyd available from Akzo Nobel
  • Akzo 11-1135 is a short oil coconut alkyd available from Akzo Nobel
  • Akzo 21-3801 is a long raw castor oil alkyd available from Akzo Nobel
  • Aroplaz 2575X60 is a short oil coconut alkyd available from Reichhold Beckosol 12-035 is a short oil coconut alkyd available from Reichhold Chempol 501-0127 is a medium oil castor oil alkyd available from CCP
  • Chempol 501-3231 is a high solids coconut oil alkyd available from CCP
  • Duramac 201-1167 is a long oil sunflower oil alkyd available from Eastman
  • Duramac 207-2742 is a chain stopped sunflower oil alkyd available from
  • Duramac 57-5816 is a long oil sunflower oil alkyd available from Eastman
  • Duramac 52-5205 is a short oil coconut oil alkyd available from Eastman
  • EPS 6560 is a medium oil coconut alkyd available from Engineered
  • Resimene 2040 was put into a formulation similar to Example 23. That formulation is given in Table 9 as comparative example 25 below.
  • Examples 26 describe the catalysis of the Example 2 coating which consists of CARBOXYMETHYL CELLULOSE ACETATE BUTYRATE/Melamine (Example 1) and Duramac 207-1205 Coconut oil alkyd with Cycat 4040, a 40% solution of para toluene sulfonic acid.
  • Example 27 describe the catalysis of the Example 3 coating which consists of Resimene 2040 and Duramac 207-1205 coconut alkyd with Cycat 4040, a 40% solution of para toluene sulfonic acid.
  • Examples 28 and 29, describe panel development for comparison of these coatings Para toluene sulfonic acid catalyzed coatings.
  • Examples 30 and 31 describe these same coating examples but catalyzed with Kcure 129B, a methane sulfonic acid catalyst available from King Industries.
  • Examples 32 and 33 detail panels developed utilizing these methane sulfonic acid catalyzed examples.
  • Example 28 CMCAB /Melamine blend formulated with Duramac 207-1205 Alkyd, shows faster cure response as a sealer resulting in significantly improved sanding; it also shows better spray flow and leveling, better print, and better mar resistance as compared to Example 29, Resimene 2040 formulated with Duramac 207-1205 Alkyd. However, Example 28 results in a less glossy film.
  • Example 32 Both Example 32, CMCAB /Melamine blend formulated with Duramac 207- 1205 Alkyd, and Example 33, Resimene 2040 formulated with Duramac 207-1205 Alkyd, catalyzed with Kcure 129B, methane sulfonic acid cure faster than these same products catalyzed with para toluene sulfonic acid; however the panel developed with Example 32, CMCAB /Melamine blend formulated with Duramac 207-1205 Alkyd, results in better initial hardness at the sealer stage, better blister resistance, better flow and leveling, better print resistance, and better slip resistance. Again, however, Example 32, CMCAB /Melamine blend formulated with Duramac 207-1205 Alkyd, results in a less glossy panel.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Paints Or Removers (AREA)

Abstract

Cette invention se rapporte à un système de réticulation aminoplast ayant une vitesse de durcissement améliorée, mesurée par des résultats de tests de résistance aux éraflures et de résistance au blocage et à l'impression. A cet effet, un ester de carboxyalkycellulose, tel que du butyrate de carboxyméthyl cellulose, est dissout dans un solvant, par exemple du méthanol ou de l'éthanol, puis mélangé avec un agent de réticulation aminoplast. Ce mélange peut être utilisé en tant que tel ou peut être ajouté à un mélange contenant une résine alkyde ou tout autre polymère compatible. Le mélange ainsi fini peut ensuite être catalysé avec un catalyseur PTSA ou avec tout autre matériau catalytique. Ce système confère à un revêtement une réaction de durcissement et une résistance à l'impression et au blocage considérablement améliorés par rapport à un agent de réticulation contenant un polyol acrylique ou un alcool allyle de styrène, tout en lui conférant de meilleurs capacités d'écoulement et de nivellement.
PCT/US2004/013983 2003-05-16 2004-05-05 Systemes de revetement reticulables contenant des esters de carboxyalkylcellulose WO2004104121A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US47104903P 2003-05-16 2003-05-16
US60/471,049 2003-05-16

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WO2004104121A1 true WO2004104121A1 (fr) 2004-12-02

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006127834A2 (fr) 2005-05-26 2006-11-30 Eastman Chemical Company Compositions d'esters cellulosiques reticulables et films obtenus
CN104892988A (zh) * 2015-05-25 2015-09-09 北京理工大学 羧甲基纤维素硝酸酯树脂水性分散体的制备方法
WO2022109230A2 (fr) 2020-11-23 2022-05-27 Sun Chemical Corporation Encres pour matières plastiques recyclables

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3411941A (en) * 1965-03-01 1968-11-19 Eastman Kodak Co Process for coating a metallic article with thermally reflowable cellulose acetate butyrate/melamine-formaldehyde resin/alkyd or acrylic resin coating compositions
WO1998033821A1 (fr) * 1996-01-29 1998-08-06 Eastman Chemical Company Esters de cellulose carboxyalkyle
US5994530A (en) * 1998-06-25 1999-11-30 Eastman Chemical Corporation Carboxyalkyl cellulose esters for use in aqueous pigment dispersions
WO2004030801A1 (fr) * 2002-10-01 2004-04-15 Eastman Chemical Company Utilisation d'esters de cellulose carboxyalkyles tels que l'acetate butyrate de cellulose carboxymethyle pour former des materiaux hydrophobes dans l'eau

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3411941A (en) * 1965-03-01 1968-11-19 Eastman Kodak Co Process for coating a metallic article with thermally reflowable cellulose acetate butyrate/melamine-formaldehyde resin/alkyd or acrylic resin coating compositions
WO1998033821A1 (fr) * 1996-01-29 1998-08-06 Eastman Chemical Company Esters de cellulose carboxyalkyle
US5994530A (en) * 1998-06-25 1999-11-30 Eastman Chemical Corporation Carboxyalkyl cellulose esters for use in aqueous pigment dispersions
WO2004030801A1 (fr) * 2002-10-01 2004-04-15 Eastman Chemical Company Utilisation d'esters de cellulose carboxyalkyles tels que l'acetate butyrate de cellulose carboxymethyle pour former des materiaux hydrophobes dans l'eau

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006127834A2 (fr) 2005-05-26 2006-11-30 Eastman Chemical Company Compositions d'esters cellulosiques reticulables et films obtenus
WO2006127834A3 (fr) * 2005-05-26 2007-06-07 Eastman Chem Co Compositions d'esters cellulosiques reticulables et films obtenus
EP2196311A3 (fr) * 2005-05-26 2010-07-07 Eastman Chemical Company Compositions d'ester de cellulose réticulables et films formés à partir de ceux-ci
US20120222793A1 (en) * 2005-05-26 2012-09-06 Eastman Chemical Company Crosslinkable, cellulose ester compositions and films formed therefrom
US8304086B2 (en) 2005-05-26 2012-11-06 Eastman Chemical Company Crosslinkable, cellulose ester compositions and films formed therefrom
US8449939B2 (en) 2005-05-26 2013-05-28 Eastman Chemical Company Crosslinkable, cellulose ester compositions and films formed therefrom
CN104892988A (zh) * 2015-05-25 2015-09-09 北京理工大学 羧甲基纤维素硝酸酯树脂水性分散体的制备方法
WO2022109230A2 (fr) 2020-11-23 2022-05-27 Sun Chemical Corporation Encres pour matières plastiques recyclables

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