EP2948459A1 - Nouveaux composés et compositions de revêtement durcissables par rayonnement - Google Patents

Nouveaux composés et compositions de revêtement durcissables par rayonnement

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Publication number
EP2948459A1
EP2948459A1 EP14700649.8A EP14700649A EP2948459A1 EP 2948459 A1 EP2948459 A1 EP 2948459A1 EP 14700649 A EP14700649 A EP 14700649A EP 2948459 A1 EP2948459 A1 EP 2948459A1
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EP
European Patent Office
Prior art keywords
hydrogen
formula
acryloyl
radiation
meth
Prior art date
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EP14700649.8A
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German (de)
English (en)
Inventor
Jürgen Baro
Monika CHARRAK
Reinhold Schwalm
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BASF SE
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BASF SE
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Priority to EP14700649.8A priority Critical patent/EP2948459A1/fr
Publication of EP2948459A1 publication Critical patent/EP2948459A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates to new radiation-curable compounds and radiation curable coating compositions comprising such compounds.
  • a very common component in radiation curable coatings is bisphenol A diglycidylether diacry- late, which is a widely used building block molecule and component in radiation curable coat- ings.
  • Bisphenol A has been known to have esterogenic properties since the 1930's.
  • R 1 and R 2 are acryloyl and the other are hydrogen and one radical out of R 3 and R 4 is acryloyl and the other is hydrogen.
  • Another object of the present invention are radiation-curable coating compositions comprising
  • (C) optionally at least one radiation-curable compound having precisely two free-radically polymerizable groups
  • (D) optionally at least one radiation-curable compound having more than two free-radically polymerizable groups.
  • Component (A) according to the invention is the new radiation curable diacrylate of formula (I),
  • R 1 and R 2 are acryloyl, and the other is hydrogen and one radical out of R 3 and R 4 is acryloyl, and the other is hydrogen.
  • Preferred components (A) are diacrylates of formula (la),
  • a very preferred component (A) is the diacrylate of formula (lb),
  • Components (A) are preferably obtainable by reaction of the corresponding glycidyl ethers of anhydrosugars with acrylic acid.
  • Reaction conditions are known to the person skilled in the art, preferably the temperature is from 23 °C to 180 °C, very preferably from 40 to 160 °C, more preferably from 60 to 140 °C and especially preferably from 80 to 120 °C for 10 minutes to 12 hours, preferably from 15 minutes to 10 hours and very preferably from 30 minutes to 8 hours.
  • a catalyst is added, e.g. tertiary amines, tertiary ammonium salts or triphenyl phosphine.
  • This reaction usually yields mixtures of acrylates as isomers.
  • mixtures of components of the above-mentioned formula (I) are obtained, in which R 1 is acryloyl and R 2 is hydro- gen, with those in which R 1 is hydrogen and R 2 is acryloyl.
  • mixtures of components of the above-mentioned formula (I) are obtained, in which R 3 is acryloyl and R 4 is hydrogen, with those in which R 3 is hydrogen and R 4 is acryloyl.
  • Such mixtures preferably consist of the isomers of formula (I) as follows
  • R 1 , R 2 , R 3 , and R 4 are acryloyl, for example on average 2 to 4, preferably 2 to 3.5, and more preferably 2.1 to 3.
  • Anhydrosugars are obtainable by dehydration of hexitols, preferably galactitol, mannitol, and glucitol and less preferred allitol, altritol und iditol.
  • the reaction is usually catalyzed by acids, preferably sulfuric acid.
  • Preferred anhydrosugars are isosorbide, isomannide, and isoidide, each of which may preferably be derived from renewable resources, such as plant-derived glucose, preferably isosorbide.
  • oligomers bearing glycidyl ether groups can be formed, which are capable of reacting with acrylic acids according to the present invention.
  • R 1 , R 2 , R 3 , and R 4 are defined as above,
  • R a is hydrogen or a radical -CH 2 -CHOR b -CH 2 OR c ,
  • R b and R c are acryloyl, and the other is hydrogen.
  • such components according to formula (lc) are based upon anhydrosugars derived from galactitol, mannitol, and glucitol and less preferred allitol, altritol und iditol, very preferably they are based on isosorbide, isomannide, and isoidide as anhydrosugars and especially preferably they are based on isosorbide.
  • Another object of the present invention are mixtures of components of formula (I) with components of formula (Ic), more preferably mixtures of components of formula (lb) with components of formula (Id).
  • Such mixtures preferably consist of
  • components of formula (le) (see below) not more than 20 wt%, preferably not more than 15 wt%, very preferably from 0.05 to 10 wt% and especially preferably from 0.1 to 5 wt%, with the proviso, that the sum always adds up to 100 wt%.
  • components of formula (lb) 60 to 99 wt%, preferably 70 to 97 wt%, very preferably 75 to 95 wt% and especially preferably 80 to 90 wt%,
  • radicals R 1 , R 2 , R a , R b , and R c , as well as n are defined as above, and n furthermore can be 0 (zero), are obtained by reaction of acrylic acid with glycidyl ethers of anhydrosugars, in which some hydroxy groups partly remain unreacted with epichlorohydrin. Such components still have free hydroxy groups.
  • Such mixtures can be used like components according to formulae (I), (lb) or (lc) alone as described herein.
  • such mixtures are obtained by reaction of acrylic acid with a mixture of glycidyl ethers of anhydrosugars and oligomers of anhydrosugars bearing glycidyl ether, wherein such mixtures of glycidyl ethers of anhydrosugars exhibit an epoxy equivalent weight of at least 200 g/eq, preferably at least 210 g/eq and very preferably at least 220 g/eq.
  • the epoxy equivalent weight of such mixtures is not more than 500 g/eq, preferably not more than 400, very preferably not more than 350 and especially not more than 300 g/eq.
  • the epoxy equivalent weight (EEW) or weight per epoxy (WPE) is the weight in grammes of resin containing 1 mole equivalent of epoxide.
  • the molar amount of epoxide is usually determined according to ASTM D 1652.
  • such glycidyl ethers of anhydrosugars optionally as a mixture with oligomers of anhydrosugars bearing glycidyl ether groups can be used to react with a surplus or unreacted acrylic acid in reaction mixtures for the production acrylic acid esters.
  • Such a process is for example disclosed in EP-A-54 105, DE-A 33 16 593, EP-A-279 303, EP-A1 921 168 and WO
  • reaction mixtures can be obtained by reaction of acrylic acid with polyols, alkoxylated polyols or polyesterols in a molar ratio hydroxy groups : acrylic acid in the esterification for example 1 : 0.75 - 2.5, preferably 1 : 0.8 - 2, more preferably 1 : 0.9 - 1 .5, and very preferably 1 : 1 - 1 .2.
  • Preferred polyols are for example trimethylolbutane, tnmethylolpropane, trimethylolethane, neopentylglycol, pentaerythntol, ethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol,
  • Preferred alkoxylated polyols are for example the above-mentioned polyols, preferably pentaerythntol, trimethylolethane or tnmethylolpropane with from single to 20-fold, more preferably from 5- to 20-fold, very preferably 10— 20-fold, and in particular 12— 20-fold ethoxylation, propoxylation or mixed ethoxylation and propoxylation, and in particular exclusively ethoxyla- tion.
  • Preferred polyesters are for example having a molar mass M n of 1000 to 4000 g/mol and are preferably synthesized from the above-recited polyols or alkoxylated polyols with di- or higher carboxylic acids.
  • Very preferred polyesters are synthesized from aliphatic diols such as ethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,1 -dimethylethane-1 ,2-diol, 2-butyl-2-ethyl-1 ,3-propanediol, 2-ethyl- 1 ,3-propanediol, 2-methyl-1 ,3-propanediol, neopentyl glycol, neopentyl glycol hydroxypivalate, 1 ,2-, 1 ,3- or 1 ,4-butanediol, 1 ,6-hexanediol, 1 ,10-decanediol, 2-ethyl-1 ,3-hexanediol, 2-propyl- 1 ,3-heptanediol, and 2,4-diethyloctane-1
  • the reaction with epoxide compounds takes place preferably at from 90 to 130°C, more preferably from 100 to 1 10 °C, and is preferably continued until the reaction mixture has an acid number to DIN EN 3682 of less than 20, more preferably less than 15, very preferably less than 10 und especially less than 5 mg KOH/g (excluding solvent).
  • Catalysts which can be used for the reaction with the epoxide compounds include, for example, quaternary ammonium compounds and phosphonium compounds, tertiary amines, phosphines such as triphenylphosphine, and Lewis bases.
  • Component (B) is at least one, one to four for example, one to three for preference, more preferably one to two, and very preferably precisely one radiation-curable compound having precisely one free-radically polymerizable group.
  • free-radically polymerizable groups are vinyl ether or ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, preferably (meth)acrylate groups, more preferably (meth)acrylate groups, and very preferably acrylate groups.
  • Monofunctional free-radically polymerizable compounds (B) are, for example, esters of ⁇ , ⁇ -ethyl-enically unsaturated carboxylic acids, preferably of (meth)acrylic acid, with alcohols containing 1 to 20 C atoms, preferably optionally hydroxyl-substituted alkanols containing 1 to 20 C atoms, e.g., methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethyl- hexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate or 4-hy- droxybutyl (meth)acrylate.
  • esters of ⁇ , ⁇ -ethyl-enically unsaturated carboxylic acids preferably of (meth)acrylic acid
  • alcohols containing 1 to 20 C atoms preferably optionally hydroxyl-substituted
  • the monoethylenically unsaturated reactive diluent (B) may preferably be a compound (B1 ), comprising at least one cycloaliphatic group, or a compound (B2), comprising at least one heterocyclic group.
  • Compounds (B1 ) are esters of (meth)acrylic acid with cycloalkanols or bicycloalkanols, the cy- cloalkanol or bicycloalkanol containing from 3 to 20 carbon atoms, preferably from 5 to 10 carbon atoms, and being optionally substituted by Ci to C 4 alkyl.
  • cycloalkanol and bicycloalkanol examples include cyclopentanol, cyclohexanol, cyclooctanol, cyclododecanol, 4-methylcyclohexanol, 4-isopropylcyclohexanol, 4-tert-butylcyclohexanol (preferably cis-configured), dihydrodicyclopentadienyl alcohol, and norbornyl alcohol. Preference is given to cyclohexanol and 4-tert-butylcyclohexanol.
  • component (B2) it is possible in principle to use all monofunctional esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids with a monofunctional alkanol that has as a structural element at least one saturated 5- or 6-membered heterocycle having one or two oxygen atoms in the ring.
  • Component (B) derives preferably from acrylic acid or methacrylic acid.
  • suitable compounds of component (B2) comprise compounds of the general formula (I II)
  • R 7 is selected from H and CH3 and more particularly is H
  • k is a number from 0 to 4 and more particularly 0 or 1
  • Y is a 5- or 6-membered, saturated heterocycle having one or two oxygen atoms, the heter- ocycle being optionally substituted by C1-C4 alkyl, e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or tert-butyl.
  • C1-C4 alkyl e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl or tert-butyl.
  • the 5- or 6-membered saturated heterocycle derives preferably from tetrahydrofuran, tetrahy- dropyran, 1 ,3-dioxolane or 1 ,3- or 1 ,4-dioxane.
  • component (B2) is selected from trimethylolpropane monoformal acrylate, glycerol monoformal acrylate, 4-tetrahydropyranyl acrylate, 2-tetrahydropyranyl methylacrylate, tetrahydrofurfuryl acrylate, and mixtures of these. Very particular preference is given to using trimethylolpropane monoformal acrylate as component (B2).
  • vinylaromatic compounds e.g., styrene, divinylbenzene, ⁇ , ⁇ -unsaturated nitriles, e.g., acrylonitrile, methacrylonitrile, ⁇ , ⁇ -unsaturated aldehydes, e.g., acrolein, methacrolein, vinyl esters, e.g., vinyl acetate, vinyl propionate, halo- genated ethylenically unsaturated compounds, e.g., vinyl chloride, vinylidene chloride, conju- gated unsaturated compounds, e.g., butadiene, isoprene, chloroprene, monounsaturated compounds, e.g., ethylene, propylene, 1 -butene, 2-butene, isobutene, cyclic monounsaturated compounds, e.g., cyclopentene
  • vinylaromatic compounds e.g.,
  • Component (C) is at least one, one to four for example, one to three for preference, more preferably one to two, and very preferably precisely one radiation-curable compound having pre- cisely two free-radically polymerizable groups.
  • Component (D) is at least one, one to four for example, one to three for preference, more preferably one to two, and very preferably precisely one radiation-curable compound having more than 2, preferably 3-10, more preferably 3-6, very preferably 3-4, and more particularly 3 free- radically polymerizable groups.
  • components (C) and (D) are selected independently of one another from the group consisting of polyfunctional (meth)acrylic esters (C1 ) and/or (D1 )
  • polyester (meth)acrylates (C2) and/or (D2) are examples of polyester (meth)acrylates (C2) and/or (D2)
  • esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids preferably of (meth)acrylic acid, more preferably of acrylic acid with polyalcohols having a corresponding functionality of at least two.
  • polyalcohols of this kind are at least dihydric polyols, polyetherols or poly- esterols or polyacrylatepolyols having an average OH functionality of at least 2, preferably 3 to 10.
  • polyfunctional polymerizable compounds (C1 ) are ethylene glycol diacrylate,
  • polyfunctional polymerizable compounds (D1 ) are trimethylolpropane triacrylate, ditrimethylolpropane pentaacrylate or hexaacrylate, pentaerythritol triacrylate or tetraacrylate, glycerol diacrylate or triacrylate, and also diacrylates and polyacrylates of sugar alcohols, such as of sorbitol, mannitol, diglycerol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), maltitol or isomalt, for example.
  • sugar alcohols such as of sorbitol, mannitol, diglycerol, threitol, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulci
  • (C1 ) and/or (D1 ) are (meth)acrylates of compounds of the formula (I la) to (lid),
  • C1-C18 alkyl optionally substituted by aryl, alkyl, aryloxy, alkyloxy, heteroa- toms and/or heterocycles is for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert- butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, 1 ,1 -dimethylpropyl, 1 ,1 -dimethylbutyl, 1 ,1 ,3,3-tetramethylbutyl, preferably methyl, ethyl or n-propyl, very preferably methyl or ethyl.
  • the compounds in question are preferably (meth)acrylates of singly to vigintuply and, more preferably, triply to decuply ethoxylated, propoxylated or mixedly ethoxylated and propoxylated, and more particularly exclusively ethoxylated, neopentyl glycol, trimethylolpropane, trime- thylolethane or pentaerythritol.
  • Preferred polyfunctional polymerizable compounds are ethylene glycol diacrylate, 1 ,2-propan- ediol diacrylate, 1 ,3-propanediol diacrylate, 1 ,4-butanediol diacrylate, 1 ,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and triacrylate of singly to vigintuply alkoxylated, more preferably ethoxylated, trimethylolpropane.
  • Polyester (meth)acrylates (C2) and/or (D2) are the corresponding esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, preferably of (meth)acrylic acid, more preferably of acrylic acid, with polyesterpolyols.
  • Polyesterpolyols are known for example from UHmanns Encyklopadie der ischen Chemie, 4th Edition, Volume 19, pp. 62 to 65. Preference is given to using polyesterpolyols obtained by reacting dihydric alcohols with dibasic carboxylic acids. In place of the free polycarboxylic acids it is also possible to use the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols, or mixtures thereof, to prepare the polyesterpolyols.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and may if desired be substituted, by halogen atoms for example, and/or unsaturated.
  • Examples thereof that may be mentioned include the following: oxalic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, sebacic acid, do- decanedioic acid, o-phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, azelaic acid, 1 ,4-cyclohexanedicarboxylic acid or tetrahydrophthalic acid, suberic acid, azelaic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, di- meric fatty acids, their isomers and hydrogenation products, and also esterifiable derivatives, such as anhydrides or dialkyl esters, such as C1-C4 alkyl esters,
  • dicarboxylic acids of the general formula HOOC-(CH2) y -COOH Preference is given to dicarboxylic acids of the general formula HOOC-(CH2) y -COOH, y being a number from 1 to 20, preferably an even number from 2 to 20, and particular preference to succinic acid, adipic acid, sebacic acid, and do- decanedicarboxylic acid.
  • Polyhydric alcohols contemplated for the preparation of the polyesterols include 1 ,2-propane- diol, ethylene glycol, 2, 2-dimethyl-1 ,2-ethanediol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,3-butane- diol, 1 ,4-butanediol, 3-methylpentane-1 ,5-diol, 2-ethylhexane-1 ,3-diol, 2,4-diethyloctane-1 ,3- diol, 1 ,6-hexanediol, polyTHF with a molar mass between 162 and 2000, poly-1 ,3-propanediol with a molar mass between 134 and 1 178, poly-1 ,2-propanediol with a molar mass between 134 and 898, polyethylene glycol with a molar mass between
  • lactone-based polyesterdiols which are homopolymers or copolymers of lac- tones, preferably hydroxyl-terminated adducts of lactones with suitable difunctional starter molecules.
  • Lactones contemplated are preferably those deriving from the compounds of the general formula HO-(CH2) z -COOH, z being a number from 1 to 20, and it also being possible for one H atom of a methylene unit to have been substituted by a Ci to C 4 alkyl radical.
  • Examples are ⁇ -caprolactone, ⁇ -propiolactone, gamma-butyrolactone and/or methyl-e-caprolactone, 4-hy- droxybenzoic acid, 6-hydroxy-2-naphthoic acid or pivalolactone, and also their mixtures.
  • Suitable starter components are, for example, the low molecular mass dihydric alcohols specified above as a synthesis component for the polyesterpolyols.
  • the corresponding polymers of ⁇ -caprolactone are particularly preferred.
  • Lower polyesterdiols or polyetherdiols can also be used as starters for preparing the lactone polymers.
  • the polymers of lactones it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxyl- carboxylic acids corresponding to the lactones.
  • Polyether (meth)acrylates (C3) and/or (D3) are the corresponding esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, preferably of (meth)acrylic acid, more preferably of acrylic acid, with polyetherols.
  • the polyetherols are preferably polyethylene glycol with a molar mass between 106 and 2000, preferably 106 to 1500, more preferably 106 to 1000, poly-1 ,2-propanediol with a molar mass between 134 and 1 178, poly-1 ,3-propanediol with a molar mass between 134 and 1 178, and polytetrahydrofurandiol having a number-average molecular weight M n in the range from about 500 to 4000, preferably 600 to 3000, more particularly 750 to 2000.
  • Urethane (meth)acrylates (C4) and/or (D4) are obtainable, for example, by reacting polyisocya- nates with hydroxyalkyl (meth)acrylates or hydroxyalkyl vinyl ethers and, if desired, chain ex- tenders such as diols, polyols, diamines, polyamines or dithiols or polythiols.
  • Urethane (meth)- acrylates dispersible in water without addition of emulsifiers additionally comprise ionic and/or nonionic hydrophilic groups, which are introduced into the urethane through synthesis components, for example, such as hydroxycarboxylic acids.
  • Such urethane (meth)acrylates substantially comprise as synthesis components:
  • the urethane (meth)acrylates preferably have a number-average molar weight M n of 500 to 20 000, more particularly of 500 to 10 000, with particular preference 600 to 3000 g/mol (as determined by gel permeation chromatography using tetrahydrofuran and polystyrene as standard).
  • the urethane (meth)acrylates preferably have a (meth)acrylic group content of 1 to 5, more preferably of 2 to 4 mol of (meth)acrylic groups per 1000 g of urethane (meth)acrylate.
  • Epoxide (meth)acrylates (C5) and/or (D5) are obtainable by reacting epoxides with (meth)acrylic acid.
  • epoxides contemplated include epoxidized olefins, aromatic glycidyl ethers or aliphatic glycidyl ethers, preferably those of aromatic or aliphatic glycidyl ethers.
  • Epoxidized olefins may for example be ethylene oxide, propylene oxide, isobutylene oxide, 1 -butene oxide, 2-butene oxide, vinyloxirane, styrene oxide or epichlorohydrin, preference being given to ethylene oxide, propylene oxide, isobutylene oxide, vinyloxirane, styrene oxide or epichlorohydrin, particular preference to ethylene oxide, propylene oxide or epichlorohydrin, and very particular preference to ethylene oxide and epichlorohydrin.
  • Aromatic glycidyl ethers are, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol B diglycidyl ether, bisphenol S diglycidyl ether, hydroquinone diglycidyl ether, alkylation products of phenol/dicyclopentadiene, e.g., 2,5-bis[(2,3-epoxypropoxy)phenyl]octa- hydro-4,7-methano-5H-indene) (CAS No. [13446-85-0]), tris[4-(2,3-epoxypropoxy)phenyl]- methane isomers) (CAS No. [66072-39-7]), phenol-based epoxy novolaks
  • Aliphatic glycidyl ethers are, for example, 1 ,4-butanediol diglycidyl ether, 1 ,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1 ,1 ,2,2-tetra- kis[4-(2,3-epoxypropoxy)phenyl]ethane (CAS No. [27043-37-4]), diglycidyl ethers of polypropylene glycol (a,(jo-bis(2,3-epoxypropoxy)poly(oxypropylene) (CAS No. [16096-30-3]) and of hy- drogenated bisphenol A (2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane,
  • the epoxide (meth)acrylates and epoxide vinyl ethers preferably have a number-average molar weight M n of 200 to 20 000, more preferably of 200 to 10 000 g/mol, and very preferably of 250 to 3000 g/mol; the (meth)acrylic group or vinyl ether group content is preferably 1 to 5, more preferably 2 to 4 per 1000 g of epoxide (meth)acrylate or vinyl ether epoxide (as determined by gel permeation chromatography using polystyrene as standard and tetrahydrofuran as eluent).
  • (Meth)acrylated polyacrylates (C6) and/or (D6) are the corresponding esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, preferably of (meth)acrylic acid, more preferably of acrylic acid, with polyacrylate polyols.
  • Polyacrylate polyols of this kind preferably have molecular weight M n of at least 1000, more preferably at least 2000, and very preferably at least 5000 g/mol.
  • the molecular weight M n can for example be up to 200 000, preferably up to 100 000, more preferably up to 80 000, and very preferably up to 50 000 g/mol.
  • Preferred OH numbers of polyacrylate polyols, measured in accordance with DIN 53240-2, are 15-250 mg KOH/g, preferably 80-160 mg KOH/g.
  • polyacrylate polyols may have an acid number in accordance with DIN EN ISO 3682 of up to 200 mg KOH/g, preferably up to 150, and more preferably up to 100 mg KOH/g.
  • the polyacrylate polyols are copolymers of at least one (meth)acrylic ester with at least one compound having at least one, preferably precisely one hydroxyl group and at least one, preferably precisely one (meth)acrylate group.
  • the latter may be, for example, monoesters of ⁇ , ⁇ -unsaturated carboxylic acids, such as acrylic acid, methacrylic acid (referred to in this document for short as "(meth)acrylic acid”), with diols or polyols, which have preferably 2 to 20 C atoms and at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,1 -dimethyl-1 ,2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, penta- ethylene glycol, tripropylene glycol, 1 ,4-butanedio
  • the monomers which carry hydroxyl groups are used in the copolymerization in a mixture with other polymerizable monomers, preferably free-radically polymerizable monomers, preferably those composed to an extent of more than 50% by weight of C1-C20, preferably Ci to C 4 alkyl (meth)acrylate, (meth)acrylic acid, vinylaromatics having up to 20 C atoms, vinyl esters of car- boxylic acids comprising up to 20 C atoms, vinyl halides, nonaromatic hydrocarbons having 4 to 8 C atoms and 1 or 2 double bonds, unsaturated nitriles, and mixtures of these.
  • Particularly preferred are the polymers composed to an extent of more than 60% by weight of Ci-Cio-alkyl (meth)acrylates, styrene, vinylimidazole or mixtures of these.
  • the polymers may further comprise hydroxyl-functional monomers corresponding to the above hydroxyl group content, and, if desired, further monomers, examples being glycidyl epoxy esters of (meth)acrylic acid, or ethylenically unsaturated acids, more particularly carboxylic acids, acid anhydrides or acid amides.
  • Carbonate (meth)acrylates (C7) and/or (D7) are likewise obtainable with different functionalities.
  • the number-average molecular weight M n of the carbonate (meth)acrylates is preferably less than 3000 g/mol, more preferably less than 1500 g/mol, more preferably less than 800 g/mol (as determined by gel permeation chromatography using polystyrene as standard; solvent: tetrahy- drofuran).
  • the carbonate (meth)acrylates are obtainable in a simple way by transesterification of carbonic esters with polyhydric, preferably dihydric, alcohols (diols, e.g., hexanediol) and subsequent esterification of the free OH groups with (meth)acrylic acid, or else transesterification with (meth)acrylic esters, as described in EP-A 92 269, for example. They are also obtainable by reaction of phosgene, urea derivatives with polyhydric alcohols, dihydric alcohols for example.
  • (meth)acrylates or vinyl ethers of polycarbonate polyols such as the reaction product of one of the stated diols or polyols and a carbonic ester and also a hydroxyl- containing (meth)acrylate or vinyl ether.
  • suitable carbonic esters are ethylene carbonate, 1 ,2- or 1 ,3-propylene carbonate, dimethyl carbonate, diethyl carbonate or dibutyl carbonate.
  • Suitable hydroxyl-containing (meth)acrylates are 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 1 ,4-butanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, glycerol mono(meth)acrylate and di(meth)acrylate, trimethylolpropane mono(meth)acrylate and di(meth)acrylate, and also pentaerythritol mono(meth)acrylate, di(meth)acrylate, and tri(meth)acrylate.
  • suitable hydroxyl-containing vinyl ethers are 2-hydroxyethyl vinyl ether and 4- hydroxybutyl vinyl ether.
  • Particularly preferred carbonate (meth)acrylates are those of the formula: in which R is H or CH3, X is a C2-C18 alkylene group, and n is an integer from 1 to 5, preferably from 1 to 3.
  • R is preferably H
  • X is preferably C 2 to C10 alkylene, exemplified by 1 ,2-ethylene, 1 ,2-pro- pylene, 1 ,3-propylene, 1 ,4-butylene or 1 ,6-hexylene, or more preferably C 4 to Cs alkylene. With very particular preference X is C6 alkylene.
  • the carbonate (meth)acrylates are prefererably aliphatic carbonate (meth)acrylates.
  • polyfunctional polymerizable compounds Particular preference among the polyfunctional polymerizable compounds is given to urethane (meth)acrylates (C4) and/or (D4).
  • At least one of the components, (C) or (D), has a diol as a synthesis component, selected from the group consisting of
  • polypropylene glycol H-[-0-CH 2 -CH(CH 3 )-] k -OH
  • polycaprolactonediol (-[-0-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -(CO)-] k -R 8 -OH), and
  • polyesterdiol (HO-[R 8 -0-(CO)-R 9 -(CO)-0-R 8 -] k -OH) with a number-average molar mass of 500 to 4000.
  • R 8 and R 9 independently of one another are a divalent aliphatic or cycloaliphatic radical having at least one carbon atom and
  • k is a positive integer needed in order to obtain the molar mass in question.
  • Preferred radicals R 8 and R 9 are, independently of one another, methylene, 1 ,2-ethylene, 1 ,2-propylene, 1 ,3-propylene, 1 ,2-, 1 ,3- or 1 ,4-butylene, 1 ,1 -dimethyl-1 ,2-ethylene or 1 ,2-di- methyl-1 ,2-ethylene, 1 ,5-pentylene, 1 ,6-hexylene, 1 ,8-octylene, 1 ,10-decylene or 1 ,12-do- decylene.
  • Diols of this kind further enhance the flexibility of the resulting coatings.
  • the coating compositions of the vention may further comprise 0% to 10% by weight of at least one photoinitiator (E).
  • Photoinitiators (E) may be, for example, photoinitiators known to the skilled worker, examples being those specified in "Advances in Polymer Science", Volume 14, Springer Berlin 1974 or in K. K. Dietliker, Chemistry and Technology of UV- and EB-Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, P. K. T. Oldring (ed.), SUA Technology Ltd, London.
  • Suitable photoinitiators are those of the kind described in WO 2006/005491 A1 , page 21 , line 18 to page 22, line 2 (corresponding to US 2006/0009589 A1 , paragraph [0150]), which is hereby incorporated by reference as part of the present disclosure.
  • nonyellowing or low-yellowing photoinitiators of the phenylglyoxalic ester type, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.
  • photoinitiators Preference among these photoinitiators is given to 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphinate, bis(2,4,6- trimethylbenzoyl)phenylphosphine oxide, benzophenone, 1 -benzoylcyclohexan-1 -ol, 2-hydroxy- 2,2-dimethylacetophenone, and 2,2-dimethoxy-2-phenylacetophenone.
  • the coating compositions of the in- vention may further comprise 0% to 10% by weight of further, typical coatings additives (F).
  • Examples of further typical coatings additives (F) that can be used include antioxidants, stabilizers, activators (accelerants), fillers, pigments, dyes, antistats, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents.
  • thermally activable initiators examples being potassium peroxodisulfate, dibenzoyl peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, azobisiso- butyronitrile, cyclohexylsulfonyl acetyl peroxide, diisopropyl percarbonate, tert-butyl peroctoate or benzpinacol, and also, for example, those thermally activable initiators which have a half-life at 80°C of more than 100 hours, such as di-tert-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, tert-butyl perbenzoate, silylated pinacols, which are available commercially under the trade name ADDID 600 from Wacker, for example, or hydroxyl-containing amine N-oxides, such as 2,2,6,6-tetramethylpiperidine-N-oxy
  • Thickeners contemplated include not only free-radically (co)polymerized (co)polymers but also typical organic and inorganic thickeners such as hydroxymethylcellulose or bentonite.
  • chelating agents which can be used include ethylenediamineacetic acid and the salts thereof, and also ⁇ -diketones.
  • Suitable fillers comprise silicates, examples being silicates obtainable by silicon tetrachloride hydrolysis, such as Aerosil ® from Degussa, silicious earth, talc, aluminum silicates, magnesium silicates, and calcium carbonates, etc.
  • Suitable stabilizers comprise typical UV absorbers such as oxanilides, triazines, and benzotria- zole (the latter available as Tinuvin ® products from Ciba-Spezialitatenchemie), and benzophe- nones.
  • Suitable free-radical scavengers examples being sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperi- dine or derivatives thereof, such as bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, for example.
  • Stabilizers are used typically in amounts from 0.1 % to 5.0% by weight, based on the solid components comprised in the preparation.
  • the coating compositions may further comprise a solvent, examples being butyl acetate, ethyl acetate, methoxypropyl acetate, toluene, xylene, fluorinated aromatics, and aliphatic and aro- matic hydrocarbon mixtures.
  • a solvent examples being butyl acetate, ethyl acetate, methoxypropyl acetate, toluene, xylene, fluorinated aromatics, and aliphatic and aro- matic hydrocarbon mixtures.
  • the coating compositions are applied free from solvent.
  • the coating compositions of the invention are suitable as molding compounds, as for example in films or tubes which may optionally be reinforced with fibers or for coating substrates such as wood, paper, textile, leather, nonwoven, plastics surfaces, glass, ceramic, mineral building materials, such as molded cement bricks and fiber cement slabs, or coated or uncoated metals, preferably plastics or metals, more particularly in the form of films or foils, and with particular preference metals.
  • substrates such as wood, paper, textile, leather, nonwoven, plastics surfaces, glass, ceramic, mineral building materials, such as molded cement bricks and fiber cement slabs, or coated or uncoated metals, preferably plastics or metals, more particularly in the form of films or foils, and with particular preference metals.
  • the coating materials can be employed in particular in primers, surfacers, pigmented topcoat materials and clearcoat materials in the field of automotive refinish or large-vehicle finishing, and aircraft. Coating materials of this kind are particularly suitable for applications requiring particularly high levels of application reliability, external weathering resistance, hardness, and flexi- bility, such as in automotive refinish large-vehicle finishing and industrial coatings.
  • the coating compositions of the invention are especially employed as or in automotive clearcoat and topcoat material(s). It is an advantage of coating compositions according to the invention that they are suitable for exterior coating, since they more colour stable than bisphenol A diglycidylether diacrylate, which tends to yellowing on exposure to UV- or daylight.
  • Coating compositions according to the present invention are furthermore useful as or for pro- ducing formulations, preferably printing inks for flexographic, screenprinting, lithographic, letterpress, gravure or ink-jet printing or in overprint varnishes.
  • the dry layer thickness in which such printing inks of the present invention are applied to the substrate differs with each printing method and can typically be up to 20 ⁇ , preferably in the range from 0.1 to 8 ⁇ , more preferably in the range from 0.2 to 7 ⁇ , even more preferably in the range from 1 to 5 ⁇ and particularly in the range from 1 to 4 ⁇ .
  • Typical printing ink layer thicknesses are 1 to 8 ⁇ for flexographic printing, 1 - 4 ⁇ for offset printing, 1 - 12 ⁇ for gravure printing.
  • Present invention printing inks for printing processes are curable by actinic radiation.
  • Actinic radiation having a wavelength range from 200 nm to 700 nm is useful for example.
  • Actinic radiation having an energy in the range from 30 mJ/cm 2 to 2000 mJ/cm 2 is useful for example.
  • Actinic radiation may advantageously be applied continuously or in the form of flashes for example.
  • a preferred embodiment of the present invention comprises effecting the curing of the printing inks by means of electron radiation in suitable electron flash devices, for example at an energy in the range from 50 to 300 keV, preferably from 90 to 200 keV.
  • suitable electron flash devices for example at an energy in the range from 50 to 300 keV, preferably from 90 to 200 keV.
  • the printing ink of the present invention preferably does not comprise any photoinitiator (E).
  • E photoinitiator
  • the distance of the electron flash devices to the printing surface is between 1 and 100 cm, preferably 2 to 50 cm.
  • Coil coating is the continuous coating of metal strips with coating materials, usually liquid coating materials.
  • Rolling metal strips after production, are wound up into rolls (referred to as “coils") for the purposes of storage and transport.
  • These metal strips represent the starting material for the majority of sheetlike metallic workpieces, examples being automobile parts, bodywork parts, instrument paneling, exterior architectural paneling, ceiling paneling or window profiles, for example.
  • the appropriate metal sheets are shaped by means of appropriate techniques such as punching, drilling, folding, profiling and/or deep drawing. Larger compo- nents, such as automobile bodywork parts, for example, are optionally assembled by welding together a number of individual parts.
  • metal strips with a thickness of 0.2 to 2 mm and a width of up to 2 m are transported at a speed of up to 200 m/min through a coil coating line, and are coated in the process.
  • a coil coating line For this purpose it is possible to use, for example, cold-rolled strips of soft steels or construction-grade steels, electrolytically galvanized thin sheet, hot-dip-galvanized steel strip, or strips of aluminum or aluminum alloys.
  • Typical lines comprise a feed station, a coil store, a cleaning and pretreatment zone, a first coating station along with baking oven and downstream cooling zone, a second coating station with oven, laminating station, and cooling, and also a coil store and winder.
  • Characteristic of coil coatings are thin films of the coating compositions, with a dry film thickness of usually well below 80 ⁇ , often below 60 ⁇ , below 50 ⁇ , and even below 40 ⁇ . Furthermore, the metal sheets are processed with a high throughput, which necessitates short residence times, i.e., necessitates drying at an elevated temperature following application of the coating, in order that the coating composition soon acquires load-bearing qualities. It may furthermore be possible to use coating compositions according to the present invention in radiation curable adhesives and in manufacturing processes of optical fibers or printed circuit board.
  • Coating of the substrates with the coating compositions of the invention takes place in accord- ance with typical processes known to the skilled worker, a coating composition of the invention or a paint formulation comprising it being applied in the desired thickness to the target substrate and optionally dried. This operation may if desired be repeated one or more times.
  • Application to the substrate may take place in a known way, as for example by spraying, troweling, knife- coating, brushing, rolling, roller coating, pouring, laminating, injection backmolding or coextrud- ing.
  • the coating material may also be applied electrostatically in the form of powder (powder coating materials).
  • a method of coating substrates which involves applying to the substrate a coating composition of the invention or a paint formulation comprising it, optionally admixed with further, typical coatings additives and thermally, chemically or radiation-curable resins, optionally drying the applied coating, curing it with electron beams or UV exposure under an oxygen- containing atmosphere or, preferably, under inert gas.
  • Radiation curing takes place with high-energy light, UV light for example, or electron beams. Radiation curing may take place at relatively high temperatures. Preference is given in that case to a temperature above the T g of the radiation-curable binder.
  • the coating materials may be applied one or more times by any of a very wide variety of spraying methods, such as compressed-air, airless or electrostatic spraying methods, using one- or two-component spraying units, or else by injecting, troweling, knifecoating, brushing, rolling, roller coating, pouring, laminating, injection backmolding or coextruding.
  • spraying methods such as compressed-air, airless or electrostatic spraying methods, using one- or two-component spraying units, or else by injecting, troweling, knifecoating, brushing, rolling, roller coating, pouring, laminating, injection backmolding or coextruding.
  • the coating thickness is generally in a range from about 3 to 1000 g/m 2 and preferably 10 to 200 g/m 2 . Drying and curing of the coatings take place generally under standard temperature conditions, i.e., without the coating being heated. Alternatively the mixtures of the invention can be used to produce coatings which, following application, are dried and cured at an elevated temperature, e.g., at 40-250°C, preferably 40-150°C, and more particularly at 40 to 100°C. This is limited by the thermal stability of the substrate.
  • a method of coating substrates which involves applying the coating composition of the invention or paint formulations comprising it, optionally admixed with thermally curable resins, to the substrate, drying it, and then curing it with electron beams or UV expo- sure under an oxygen-containing atmosphere or, preferably, under inert gas, optionally at temperatures up to the level of the drying temperature.
  • drying and/or radiation curing may optionally take place after each coating operation.
  • suitable radiation sources for the radiation cure are low-pressure, medium- pressure, and high-pressure mercury lamps, and also fluorescent tubes, pulsed lamps, metal halide lamps, electronic flash devices, which allow radiation curing without a photoinitiator, or excimer lamps.
  • radiation sources used include high-pressure mercury vapor lamps, lasers, pulsed lamps (flash light), halogen lamps or excimer lamps.
  • the radiation dose typically sufficient for crosslinking in the case of UV curing is situated in the range from 80 to 3000 mJ/cm 2 .
  • Drying and/or thermal treatment may also take place, in addition to or instead of the thermal treatment, by means of NIR radiation, which here refers to electromagnetic radiation in the wavelength range from 760 nm to 2.5 ⁇ , preferably from 900 to 1500 nm.
  • NIR radiation refers to electromagnetic radiation in the wavelength range from 760 nm to 2.5 ⁇ , preferably from 900 to 1500 nm.
  • Irradiation can optionally also be carried out in the absence of oxygen, such as under an inert gas atmosphere.
  • Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide, or combustion gases.
  • irradiation may take place with the coating composition being covered with transparent media.
  • transparent media are polymeric films, glass or liquids, water for example. Particular preference is given to irradiation in the manner described in DE-A1 199 57 900.
  • Isosorbid diglycidylether was prepared in an analogous matter to the method of Polymer 52 (201 1 ), 3612 by reaction of 4 mol isosorbid with 40 mol epichlorohydrin. The mixture was heated to 1 15°C to reflux under nitrogen. An aqueous solution of 8 mol sodium hydroxide was con- tinuosly added over 4 hours. Afterwards, water and unreacted epichlorohydrin was distilled off in vacuo. The resulting viscous product isosorbid diglycidylether has a weight per epoxy (WPE) of 235 g/eq.
  • WPE weight per epoxy
  • the product thus obtained consists mainly of isosorbid diglycidylether with minor amounts of the component of two isosorbid molecules, coupled together via a 2-hydroxy-1 ,3-propylene link, bearing two diglycidylether groups, and traces of the component of two isosorbid molecules, coupled together via 2-hydroxy-1 ,3-propylene link, bearing one diglycidylether group and one hydroxy group of an isosorbid moiety remaining free.
  • a formulation was prepared by blending 80 parts of the product of Example 1 , 20 parts butyl acetate and 3.2 parts of the photoinitiator Irgacure® 500 (BASF SE, Ludwigshafen, 1 :1 mixture by weight of 2-hydroxy-2-methyl-1 -phenylpropan-1 -one and benzophenone).
  • the resultant varnish formulations were applied to Bonder panel using a 100 ⁇ box-type coating bar, dried for 1 hour at 60 °C, and were exposed in an IST-UV belt unit at 1350 mJ/cm 2 under air in each case.
  • the glass transition temperature of the thus obtained coating was determined to 54 °C (measured by DSC, heating rate 10 K/min).
  • a formulation was prepared by blending 70 parts of the product of Example 1 , 30 parts dipro- pylenglycol diacrylate and 4 parts of the photoinitiator Irgacure® 500 (BASF SE, Ludwigshafen, 1 :1 mixture by weight of 2-hydroxy-2-methyl-1 -phenylpropan-1 -one and benzophenone).
  • the resultant varnish formulation was applied to Bonder panel using a 100 ⁇ box-type coating bar, dried for 1 hour at 60 °C, and were exposed in an IST-UV belt unit at 1350 mJ/cm 2 under air in each case.
  • the thus obtained coating exhibited a pendulum damping of 161 seconds (according to DIN 53157, high values represent a high hardness) and an Erichsen cupping of 2.8 mm (according to DIN 53156, high values represent a high flexibility).
  • a formulation was prepared by blending 70 parts of the diacrylate of bisphenol A diglycidylether diacrylate ("BADGE-DA ", obtained by reaction of Epikote® 828 (diglycidyl ether of bisphenol A, epoxy equivalent weight (EEW) 186 g/eq, Hexion Specialty Chemicals B.V., Hoogvliet, The Netherlands) and 2 equivalents acrylic acid), 30 parts dipropylenglycol diacrylate and 4 parts of the photoinitiator Irgacure® 500 (BASF SE, Ludwigshafen, 1 :1 mixture by weight of 2-hydroxy- 2-methyl-1 -phenylpropan-1 -one and benzophenone).
  • the resultant varnish formulation was applied to Bonder panel using a 100 ⁇ box-type coating bar, dried for 1 hour at 60 °C, and were exposed in an IST-UV belt unit at 1350 mJ/cm 2 under air in each case.
  • the thus obtained coating exhibited a pendulum damping of 203 seconds and an Erichsen cupping of 1.6 mm.
  • Example 3 Comparative Example 3 and Comparative Example 4 were applied to Bonder panels, using a 100 ⁇ box-type coating bar and black glass plates, using a 50 ⁇ box-type coating bar, respectively, dried for 1 hour at room temperature, and were exposed in an IST-UV belt unit at 1350 mJ/cm 2 under air in each case.
  • a formulation was prepared by blending 70 parts of of the reaction product of standard Bi- sphenol-A-diglycidylether (EEW 241 g/eq) with acrylic acid, 30 parts dipropylenglycol diacrylate and 4 parts of the photoinitiator Irgacure® 500 (BASF SE, Ludwigshafen, 1 :1 mixture by weight of 2-hydroxy-2-methyl-1 -phenylpropan-1 -one and benzophenone).
  • a formulation was prepared by blending 70 parts of the reaction product of standard Bis- phenol-A-diglycidylether (EEW 186 g/eq) with acrylic acid, 30 parts dipropylenglycol diacrylate and 4 parts of the photoinitiator Irgacure® 500 (BASF SE, Ludwigshafen, 1 :1 mixture by weight of 2-hydroxy-2-methyl-1 -phenylpropan-1 -one and benzophenone).
  • the inventive ISDGE-DA (formulation a)) is at high enough hardness and comparable scratch resistance more flexible than the comparative epoxy acrylates based on Bisphenole A chemistry.

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Abstract

La présente invention concerne de nouveaux composés durcissables par rayonnement et des compositions de revêtement durcissables par rayonnement comprenant de tels composés.
EP14700649.8A 2013-01-25 2014-01-15 Nouveaux composés et compositions de revêtement durcissables par rayonnement Withdrawn EP2948459A1 (fr)

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WO2019122257A1 (fr) 2017-12-21 2019-06-27 Elantas Europe S.R.L. Nouvelle utilisation de l'isosorbide
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