WO2002046252A1 - Compositions de revetement a forte teneur en solides durcissables par irradiation et preparation de ces dernieres - Google Patents

Compositions de revetement a forte teneur en solides durcissables par irradiation et preparation de ces dernieres Download PDF

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Publication number
WO2002046252A1
WO2002046252A1 PCT/EP2001/013412 EP0113412W WO0246252A1 WO 2002046252 A1 WO2002046252 A1 WO 2002046252A1 EP 0113412 W EP0113412 W EP 0113412W WO 0246252 A1 WO0246252 A1 WO 0246252A1
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WIPO (PCT)
Prior art keywords
optionally
carbon atoms
adduct
low viscosity
copolymer binder
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PCT/EP2001/013412
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English (en)
Inventor
Jean-Marc Jacques Eric Bertens
Helene Marie Jacqueline Claude Petit
Henricus Paulus Hubertus Scholten
Griet Uytterhoeven
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Resolution Research Nederland B.V.
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Application filed by Resolution Research Nederland B.V. filed Critical Resolution Research Nederland B.V.
Priority to AU2002221870A priority Critical patent/AU2002221870A1/en
Publication of WO2002046252A1 publication Critical patent/WO2002046252A1/fr

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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate

Definitions

  • the invention relates to irradiation curable high solid coating compositions and their preparation.
  • the invention relates to high solid coating compositions derived from epoxy compounds and an ethylenically unsaturated acid, which can be cured by ultraviolet light, optionally in combination with a heat source e.g. infrared light, after application on the desired substrate.
  • a heat source e.g. infrared light
  • Another object of the invention was to develop solvent free high solid coating compositions, derived from less different ingredients, which moreover should be as cheap as possible.
  • a coating composition aimed at and a copolymer binder to be used in it have been surprisingly found now.
  • the present invention relates to a low viscosity copolymer binder, containing hydroxyl groups, obtainable by copolymerization in the absence of solvents or in the presence of small amounts of inert organic solvent, of at least:
  • the polymerization is be carried out at a temperature in the range from 40 to 80 °C and preferably from 60 to 70 °C. Relatively high temperatures in this range can be reached by the use of additional IR light sources, e.g. from 5 to 10 IR lamps of 600 W, providing additional heat for reaching desired temperatures in the coating layer.
  • additional IR light sources e.g. from 5 to 10 IR lamps of 600 W
  • Suitable UV irradiation densities for the curing of the compositions of the present invention are in the range of from 50 to 1700 J/m.2.
  • UV irradiation densities used in the range of from 200 to 1200 J/m.2 and more preferably from 500 to 1000 J/m 2 .
  • the adduct component (1) is initially prepared from (A) and (B) , in about equimolar amounts, in the presence of a catalyst, known in the art for this purpose, such as stannous octoate, in an amount of from 0.01 to 0.20 wt%, and preferably 0.05 to 0.10 wt%, relative to the weight of component A, and in the presence of a polymerization inhibitor, such as hydroquinone derivatives in an amount of from 100 to 200 pp relative to the weight of component A, at a temperature in the range of from 50 °C to 200 °C, and preferably from 80 °C to 100 °C.
  • a catalyst known in the art for this purpose, such as stannous octoate
  • a polymerization inhibitor such as hydroquinone derivatives
  • the preferred component (B) is acrylic acid.
  • Optional comonomers (2) may be selected from di- or tri-acrylates of polyols, such as tripropylene glycol diacrylate, trimethylol propane triacrylate, bis-phenylol propane acrylate, hexane diol diacrylate, and relatively small amounts of silicone acrylates, such as EBECRYL 350 (EBECRYL is a trademark) and/or amino acrylate (e.g. EBECRYL 7100) in total amounts of from 10-80 wt%, relative to the total weight of comonomers .
  • EBECRYL 350 EBECRYL is a trademark
  • amino acrylate e.g. EBECRYL 7100
  • Additional suitable comonomers as component (2) are selected from, alkyl acrylates and hydroxy alkyl acrylates, wherein the alkyl ester group contains from 1 to 4 carbon atoms and wherein the acrylate residue can be optionally ⁇ -substituted by an alkyl group of from 1 to 4 carbon atoms; vinyl aromatic comonomers having from 8 to 20 carbon atoms and preferably styrene.
  • coating compositions derived from the (co) polymer binders as specified hereinbefore show a very attractive adhesion to metal, wood, paper and polymer substrates, and in particular to poly (propylene) , poly (ethylene) , optionally mixed with propylene-, ethylene-, alkadiene-copolymers (EPDM) or alkadiene-vinyl aromatic block copolymers .
  • Another surprising advantage provided by the hereinbefore specified (co) polymer binders was the attractive low viscosity, which enables the use of less or no diluent comonomers in comparison to prior art compositions.
  • the concentration of photo-initiator is in the range of from 1 to 8 wt%, and preferably from 2 to 7 wt%, relative to the weight of the total (co) onomer composition and most preferably from 3 to 6 wt% .
  • the polymerization temperature is in the range of from 60 to 70 °C.
  • the curable low ' iscosity binders of the present invention may contain, in addition to the hereinbefore defined adducts, acrylate comonomers in amounts of from 10 to 80 wt%, relative to the weight of the total composition and preferably from 20 to 70 wt% and more preferably from 30 to 60 wt% .
  • the copolymerisation is carried out without any solvent.
  • the use of small amounts of inert organic solvent may be desired (i.e. amounts of at most 5 wt%, relative to the weight of the complete comonomer composition) .
  • the diglycidyl esters of ⁇ , ⁇ , ⁇ ' , ⁇ ' -branched aliphatic dicarboxylic acids (DTADGE) used for the (co) polymers binders of the present invention are more in particular diglycidylesters of ⁇ , ⁇ , ⁇ ' , ⁇ ' -tetraalkylalkanedicarboxylic acids, containing from 8 to 18 carbon atoms in the acid moiety, and more preferably from 10 to 14 carbon atoms.
  • Most preferred starting components A are selected from diglycidylesters of and technical mixtures thereof straightly obtainable from commercial manufacturing processes.
  • the ⁇ , ⁇ , ⁇ ' , ⁇ ' -branched aliphatic dicarboxylic acids (DTA) used as components (c) are more in particular those, containing from 8 to 18 carbon atoms in the acid moiety and preferably from 10 to 14 carbon atoms. More preferred as diacids are those produced as technical mixtures straightly obtained from commercial manufacturing processes.
  • Suitable photo-initiators which can be used for the manufacture of the high solid copolymer systems according to the present invention are soluble in the starting (co) monomer (s) compositions.
  • Such photo-initiators are e.g. those composed of (a) an aromatic ketone, (b) optionally one or more tertiary amines, at least one carbon of which, situated in the alpha position with regard to the nitrogen atom, carries at least one hydrogen atom, and (c) at least one aromatic or non-aromatic alpha dione.
  • Aromatic ketones which can be used include acetophenone, propiophenone, 2-phenyl-acetophenone,
  • tertiary amines having at least one hydrogen atom on the carbon atom next to the nitrogen atom.
  • Tertiary amines which can be used include trimethylamine, triethanolamine, N-methyldiethanolamine, N,N' -dimethyl-ethanolamine, dimethylstearylamine,
  • the photo-initiating action of the above-mentioned aromatic ketones can also be greatly improved by the addition of at least one aromatic or non-aromatic alphadione, examples of which include biacetyl, glyoxal, indane-1, 2-dione, p-chlorophenyl-glyoxal, benzil, camphoquinone and the like.
  • Photo-initiator compositions derived from the components (a), (b) and (c) contain from 0.5 to 95 wt% of (a), from 0 to 99 wt% of (b) , and from 0 to 90 wt% of (c) .
  • the tertiary amine function at least one carbon atom of which, in the alpha position with regard to the nitrogen atom, carries at least one hydrogen atom
  • the aromatic ketone function for example 2-isopropyloxy-2- (4-dimethyl- aminophenyl) -propiophenone, 4-dimethylaminobenzophenone, 4,4' -bis- (dimethylamino) -benzophenone, N-methylacridone, 2-diethylamino-9-fluorenone, 7-diethylamino- -methyl- coumarin and the like.
  • the tertiary amine function at least one carbon atom of which, in the alpha position with regard to the nitrogen atom, carries at least one hydrogen atom
  • at least one acrylic or methacrylic radical for example the monoacrylates, diacrylates and triacrylates or methacrylates of triethanolamine, N-methyl-diethanolamine, N,N' -dimethyl- ethanolamine or N,N' -di (2-hydroxyethyl) -aniline; or the mixed esters of acrylic acid and beta-dimethylamino- propionic acid with polyols, such as 1, -butanediol, trimethylolpropane or the like.
  • the hereinbefore specified photo-initiators can be applied in concentrations of 1 to 25 wt% of the weight of the total composition.
  • More specific examples are oligo (2-hydroxy-2-methyl- 1- (4- (l-methylvinyl)phenyl)propanone) , 2-hydroxy-2- methyl-1-phenyl-l-propanone, 2, 4, 6-trimethylbenzophenone, 4-methylbenzophenone, 2, 2-dimethoxy-l, 2-diphenylethanone, 2-butoxy-l, 2-diphenylethanone, 2-(2-methyl propoxy) -1, 2- diphenylethanone, benzophenone, 2-alpha hydroxy ketone, other alpha hydroxy ketones, other benzophenone derivatives or mixtures thereof.
  • photo-initiators i.e., photo-polymerization initiators
  • suitable photo-initiators are listed in U.S. Patent No. 4,670,295 (Quin et al . ) and U.S. Patent No. 4,680,368 (Nakamoto et al . ) .
  • a preferred photo-initiators is ESACURE KIP-100F (ESACURE is a trademark) that is commercially available from Sartomer.
  • This photo-initiator (ESACURE KIP-100F) is a liquid mixture of 70% by weigh of oligo (2-hydroxy-2- methyl-1- (4- (1-methylvinyl) phenyl) propanone with a
  • Said photo-initiators are preferably used in amounts of from 0.05 to 5 wt% relative to the weight of the total composition, and more preferably from 0.1 to 0.5 wt% .
  • photo- initiators include, but are not limited to 1-hydroxy cyclohexyl phenyl ketone (IRGACURE 184); n 5 -2, 4-cyclo- pentadien-1-yl) (1, 2, 3, 4, 5, 6-n) - (1-methyl ethyl) benzene) - iron (+) -hexafluorophosphate (-1) (IRGACURE 261); 2-benzyl-2-n-dimethylamino-l- (4-morpholinophenyl) -1- butanone (IRGACURE 369) ; 1-hydroxycyclohexyl phenyl ketone (50% by weight) plus benzophenone (50% by weight) (IRGACURE 500); bis (2, 6-dimethoxy benzoyl) -2, 4, 4-tri- methylpentyl phosphineoxide (DMBAPO) (25% by weight) plus 2-hydroxy-2-methyl-l-phenyl-propan-l-one (HMMP)
  • Preferred curable binder compositions according to the present invention are those wherein adducts of diglycidylesters of ⁇ , ⁇ , ⁇ ' , ⁇ ' -branched aliphatic dicarboxylic acids (DTADGE) and acrylic acid in an about 1:1 molar ratio have been used in combination with tripropylene glycol diacrylate, trimethylol propane triacrylate, hexanedioldiacrylate, optionally mixed with minor amounts of aminoacrylatee, e.g. EBECRYL 7100 and/or silicone acrylate (e.g. EBECRYL 350) .
  • DTADGE diglycidylesters of ⁇ , ⁇ , ⁇ ' , ⁇ ' -branched aliphatic dicarboxylic acids
  • acrylic acid in an about 1:1 molar ratio
  • tripropylene glycol diacrylate trimethylol propane triacrylate
  • hexanedioldiacrylate optionally mixed with minor amounts of aminoacrylatee, e.g. EB
  • irradiation curable coating compositions comprising at least one comonomer (1) and optionally comonomer (2), and a free radical polymerization photo-initiator as specified hereinbefore, and optionally one or more of the usual auxiliaries such as dyes, coloring agents, stabilisers and the like.
  • the invention moreover relates to irradiation cured coating films on a substrate, comprising a copolymer binder as specified hereinbefore.
  • Said coating compositions have been surprisingly found to provide an excellent adhesion to pure poly (propylene) , pure poly (ethylene) poly (propylene) mixed with ethylenepropylene diene rubber (EPDM) , poly (propylene) mixed with optionally hydrogenated with alkadiene-vinyl aromatic block copolymers and non-treated or pretreated metal surfaces but also to wooden or paper substrates and in particular wooden construction elements for the building industry.
  • the curing of said coating compositions is preferably carried out by means of UV, visible light, optionally in combination with IR radiation.
  • the coated articles are transported on a conveyor moving under fixed irradiation sources with an adjusted speed.
  • the present invention also relates to articles, coated with compositions comprising at least one (co) olymer binder according to the invention, in a cured or uncured state.
  • thermosetting coating composition containing low mol weight hydroxy functional acrylic copolymer, linear low molecular weight hydroxy functional polyester polymer and a hydroxy ester functional epoxy ester diluent, produced by copolymerizing ethylenically unsaturated monomers containing glycidyl or oxirane functional monomers, such as acrylic, methacrylic or vinyl derivatives of glycidol .
  • Said diluent could be prepared from a diglyciyl ester of 2, 2-dimethyl-4-methylene glutarate and a saturated or unsaturated fatty acids.
  • organic solvents were used in significant amounts during preparation of the respective ingredients, and which had to be stripped off to increase the polymer solids content. The invention is illustrated in more detail in the following examples, however without restricting its scope to these specific embodiments.
  • the reactor charge is heated slowly under constant stirring to ⁇ 80 °C, where a big exotherm appears.
  • the temperature will increase to 100 °C and this temperature is maintained, until the exotherm is stabilised and a final epoxy group content (EGC) is reached of 17 meq/kg.
  • the viscosity of the DTADGE-AA adduct is 13500 mPas at 20 °C.
  • DABCO T9 catalyst (0.07 wt% on GMA) 0.0735 MMHQ (monomethylether of hydroquinone) as inhibitor (185 ppm on GMA) 0.0194
  • DTA ditertiary acid
  • glycidyl methacrylate a commercial grade of stannous octoate
  • 0.07 wt% DABCO T9 a commercial grade of stannous octoate
  • the reactor charge is heated slowly under constant stirring to -80 °C, where an exotherm appears.
  • the temperature will increase to 100 °C and this temperature is maintained, until the exotherm is stabilised.
  • composition normally comprises: Epoxy acrylate (E828-AA adduct)
  • TPGDA Tripropylene glycol diacrylate
  • TMPTA Trimethylol propane triacrylate
  • HDDA Hexanedioldiacrylate
  • IRGACURE 500 (mix of benzophenone and IRGACURE 184) 5.5%
  • This recipe has to be used ideally at a temperature of 60 °C (heat given by one or more IR lamps of 600 W each) .
  • Speed of the conveyor 40/50 m/min.
  • composition (III) was prepared comprising: DTADGE-AA adduct 37.5% by weight tripropylene glycol diacrylate (TPGDA) 25% trimethylol propane triacrylate (TMPTA) 10% hexanediol acrylate (HDDA) 8% aminoacrylate (EBECRYL 7100) 13% silicone acrylate (EBECRYL 350) 1%
  • composition (IV) was prepared comprising:
  • composition (V) was prepared comprising: DTADGE-AA adduct 94.5% by weight IRGACURE 500 5.5%
  • Example 6
  • composition (VI) was prepared comprising:
  • composition (B) was prepared comprising:
  • composition (VII) was prepared comprising:
  • composition (C) was prepared comprising: EBECRYL 600 37.5% by weight
  • composition (IX) was prepared comprising: GMA-DTA adduct 37.5% by weight TPGDA 25%
  • compositions III-IX and comparative compositions A-C were tested on different substrates pure polypropylene, modified polypropylene mixed with ethylene propylene diene rubber (EPDM) and metal Q-panels .
  • a temperature of in average of 60 °C was aimed when applying heat from 9 IR lamps of 600 W each.
  • the UV irradiation was delivered by a 120 bulb H lamp, providing an irradiation energy density of

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Selon l'invention, un liant copolymère à faible viscosité, comportant des groupes hydroxyles, peut être obtenu par une copolymérisation, effectuée sans solvant ou avec de faibles quantités d'un solvant organique inerte, d'au moins : 1) un adduit composé (A) d'un ou plusieurs diglycidyléthers d'acides dicarboxyliques aliphatiques-α, α, α', α' ramifiés, comportant de 8 à 18 atomes de carbone dans le résidu d'acide, et de préférence de 10 à 14 atomes de carbone (DTADGE) ; (B) d'acide acrylique, éventuellement d'un alkyle-α substitué, le substituant de l'alkyle contenant entre 1 et 4 atomes de carbone, et de préférence 1 atome de carbone, le rapport molaire de A et de B allant de 0,9 à 1,1 et de 1,1 à 0,9, mais se rapprochant de préférence de 1,0 ; (C) d'un ou plusieurs acides dicarboxyliques aliphatiques-α, α, α', α' ramifiés (DTA) ; et (D) d'acrylate de glycidyle, le résidu d'acide acrylique ayant été éventuellement substitué par un alkyle contenant entre 1 et 4 atomes de carbone, et de préférence 1 atome de carbone, le rapport molaire de (C) et de (D) allant de 0,9 à 1,0, mais se rapprochant de préférence de 1,0 ; et (2) éventuellement d'un ou plusieurs comonomères éthylèniquement insaturés autres que l'adduit ci-décrit. Ladite copolymérisation est effectuée en présence d'un photo-initiateur (3) de polymérisation radicalaire, et sous un rayonnement d'ultraviolets et de lumière infrarouge. L'invention concerne également des compositions de revêtement durcissables par irradiation, comprenant les composants 1 et 3 ci-décrits, et éventuellement le composant 2, ainsi que des films de revêtement durcis sur un substrat.
PCT/EP2001/013412 2000-12-08 2001-11-16 Compositions de revetement a forte teneur en solides durcissables par irradiation et preparation de ces dernieres WO2002046252A1 (fr)

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AU2002221870A AU2002221870A1 (en) 2000-12-08 2001-11-16 Irradiation curable, high solid coating compositions and their preparation

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EP00204394 2000-12-08
EP00204394.1 2000-12-08

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0027931A1 (fr) * 1979-10-19 1981-05-06 Hoechst Aktiengesellschaft Procédé de préparation de copolymères contenant des groupes OH et leur utilisation
EP0680977A1 (fr) * 1994-05-02 1995-11-08 Hoechst Aktiengesellschaft Copolymères contenants des groupes hydroxyliques et carboxyliques, leur préparation et leur usage dans des revêtements à haute teneur en solides
EP0856533A1 (fr) * 1997-02-04 1998-08-05 Herberts Gesellschaft mit beschränkter Haftung Polymères contenant des groupes hydroxyl et un procédé pour leur préparation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0027931A1 (fr) * 1979-10-19 1981-05-06 Hoechst Aktiengesellschaft Procédé de préparation de copolymères contenant des groupes OH et leur utilisation
EP0680977A1 (fr) * 1994-05-02 1995-11-08 Hoechst Aktiengesellschaft Copolymères contenants des groupes hydroxyliques et carboxyliques, leur préparation et leur usage dans des revêtements à haute teneur en solides
EP0856533A1 (fr) * 1997-02-04 1998-08-05 Herberts Gesellschaft mit beschränkter Haftung Polymères contenant des groupes hydroxyl et un procédé pour leur préparation

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