EP4204462A1 - Procédé de séchage uv de dispersions de peinture de polyuréthane à base d'eau sans initiateurs de surface pouvant être activés par uv-c - Google Patents

Procédé de séchage uv de dispersions de peinture de polyuréthane à base d'eau sans initiateurs de surface pouvant être activés par uv-c

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Publication number
EP4204462A1
EP4204462A1 EP21766434.1A EP21766434A EP4204462A1 EP 4204462 A1 EP4204462 A1 EP 4204462A1 EP 21766434 A EP21766434 A EP 21766434A EP 4204462 A1 EP4204462 A1 EP 4204462A1
Authority
EP
European Patent Office
Prior art keywords
paint formulation
meth
acrylates
paint
diol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21766434.1A
Other languages
German (de)
English (en)
Inventor
Axel Becker
Oliver Starzmann
Michael Stengle
Frederik FEIL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
IST Metz GmbH
Original Assignee
BASF SE
IST Metz GmbH
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 BASF SE, IST Metz GmbH filed Critical BASF SE
Publication of EP4204462A1 publication Critical patent/EP4204462A1/fr
Pending legal-status Critical Current

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Classifications

    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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 a method for producing a paint coating on a flat substrate by UV curing of a water-based paint formulation comprising an aqueous dispersion of urethane (meth)acrylates, in particular on substrates such as paper, wood, woodbase materials, metals, and plastics.
  • Coating systems cured by exposure to actinic radiation are formulations comprising oligomers or polymers having a plurality of ethylenically unsaturated double bonds, commonly present in the form of acrylate groups or methacrylate groups, and optionally low-molecular-weight ethylenically unsaturated monomers.
  • the formulations are applied to the substrate surface to be coated and cured by irradiating with actinic radiation or else with electron beams. What takes place here is a free-radical polymerization of the ethylenically unsaturated double bonds to form a crosslinked polymer film.
  • the curing of photosensitive mixtures with UV radiation involves the addition to the coating compositions of photoinitiators that absorb the UV radiation, generate radicals or protons, and initiate photopolymerization or photocrosslinking.
  • the amount of photoinitiator added for this purpose is > 0.5% by weight of the curable unsaturated compounds, often > 1 % by weight.
  • UV curing under an inert gas atmosphere allows the amount of photoinitiator required to be reduced.
  • the presence of atmospheric oxygen inhibits the photopolymerization, since reactive oxygen, which is itself a diradical, scavenges the radicals formed from the photoinitiator or during the free-radical polymerization, thereby taking them out of the polymerization reaction.
  • WO 01/27207 A1 discloses the curing of a paint formulation comprising 25 parts by weight of polyether acrylate and 75 parts by weight of an aqueous polyurethane dispersion using a high- pressure mercury lamp at a power of 120 W/cm.
  • a photocurable paint formulation comprising a photoinitiator is often more unstable than a corresponding formulation without photoinitiator. Since photoinitiators rank among the costly constituents of UV-curable paint formulations, it is advantageous for the amounts of photoinitiators in UV-curable paint formulations to be only small. Moreover, photoinitiators and fragments thereof that form on irradiation with UV light often result in yellowing of the paint films or obtrusive odors due to volatile substances. There may also be toxicological concerns about the use of photoinitiators. Furniture manufacturers accordingly impose strict requirements on the type and amount of photoinitiators used in UV-curable paint coatings.
  • the object of the invention is to provide water-based UV-curable paint formulations in which photoinitiators or particular types of photoinitiators are present only in small amounts or are absent altogether, and also to provide a method for producing paint coatings on a flat substrate by UV curing of the water-based paint formulations, wherein curing may in particular be carried out in air too.
  • the object is achieved by a method for producing a paint coating on a substrate by UV curing of a water-based paint formulation comprising an aqueous dispersion of urethane (meth)acrylates, said method comprising the steps in the sequence (i) to (iv):
  • the curing of the paint formulation with UV-C light in step (iii) uses according to the invention a UV radiation source that in the UV-C range from 180 to 280 nm, in particular in the range from 180 to 240 nm, has a distinctly higher power output compared with conventional UV-C radiation sources.
  • the radiation source used is according to the invention a mercury lamp, in particular, a medium-pressure mercury lamp.
  • the mercury lamp has according to the invention an electrical power consumption (power input) of > 150 W/cm, preferably > 180 W/cm.
  • an undoped mercury lamp is used.
  • the mercury lamp used according to the invention is constructed in the form of a hollow cylinder, the jacket tube of which is made of a material that is transparent to UV radiation.
  • the hollow cylinder is sealed at its end faces, with the result that the interior of the hollow cylinder forms a closed volume in which a filling gas is enclosed.
  • the hollow cylinder has electrical connections at least at its end faces for transferring energy into the filling gas in the interior of the hollow cylinder.
  • the filling gas consists of at least one noble gas and a proportion of mercury, it being possible for the filling gas to additionally be doped with proportions of other metals. Doping may be for example with lead, iron, gallium, indium or other metals, according to individual requirement.
  • the jacket tube of the mercury lamp has in accordance with the invention high transparency for shortwave UV radiation in the 180 to 240 nm range. It is preferable that the jacket tube is made of a quartz material having high transparency to IIV-C.
  • the jacket tube has high thermal stability.
  • the quartz material used can for example be one of the Suprasil series type from Heraeus, for example Suprasil 3001 13002 I 300.
  • the filling gas has in operation a working pressure within a range from 1 bar to 10 bar, preferably within a range from 1.5 bar to 8 bar, more preferably within a range from 1.7 bar to 5 bar.
  • the working voltage per cm arc length is within a range from 5 V/cm to 30 V/cm, preferably from 8 V/cm to 20 V/cm, more preferably within a range from 10 V/cm to 15 V/cm.
  • the electrical power input of the mercury lamp per cm arc length is in general within a range from 150 to 500 W/cm, preferably within a range from 180 to 500 W/cm, more preferably within a range from 200 to 500 W/cm, even more preferably within a range from 200 to 400 W/cm, in particular within a range from 200 to 350 W/cm.
  • the current and voltage per cm arc length are in accordance with the invention optimized for a maximum output in the 180 to 240 nm UV range; the conversion efficiency for this wavelength range is > 13%, preferably > 15%, more preferably > 17%, based on the power input.
  • the UV-C output per cm arc length in the 180 to 240 nm range is thus in accordance with the invention at least 19.5 W/cm, preferably at least 22.5 W/cm, and more preferably at least 25.5 W/cm or at least 23.4 W/cm, preferably at least 27 W/cm and more preferably at least 30.6 W/cm.
  • a conversion efficiency of 15% it is in general within a range from 22.5 to 75 W/cm, preferably within a range from 27 to 75 W/cm, more preferably within a range from 30 to 75 W/cm, even more preferably within a range from 30 to 60 W/cm, and in particular within a range from 30 to 52.5 W/cm.
  • the radiation unit accordingly has reflectors for deflecting light of the shortwave radiation emitted by the radiation source into the process plane.
  • the reflectors reflect UV radiation in the 180 to 240 nm range, preferably in the 180 nm to 300 nm range, more preferably in the 180 nm to 400 nm range.
  • the reflectance of the reflectors in the 180 to 240 nm range is in particular greater than or equal to 80%, preferably greater than 90%, more preferably greater than 95%.
  • the reflectors may be metallic reflectors, for example aluminum reflectors, dielectric reflectors or combinations of metallic and dielectric reflectors.
  • the reflectors may have focusing, scattering or collimating properties.
  • Further optical elements for the deflection of light may be provided, for example lenses or diffractive elements.
  • the IIV-C curing (iii) of the dried paint film with the mercury lamp used according to the invention can be carried out in the absence of so-called surface photoinitiators activatable with IIV-C light and in the presence of oxygen, i.e. without an inert gas atmosphere.
  • curing step (iii) is carried out in air.
  • Photoinitiators activatable by UV radiation having a wavelength of > 350 nm which generally serve as initiators for the surface curing of pigmented paints, generally have an absorption band with a maximum within a range from 260 to 340 nm.
  • alpha-hydroxy- alkylphenones and alpha-dialkoxyacetophenones such as 1 -hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1 -propanone, 2- hydroxy-1 - ⁇ 4-[4-(2-hydroxy-2-methylpropio- nyl)benzyl]phenyl ⁇ -2-methylpropan-1-one, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1- propanone or 2, 2-dimethoxy-1 -phenylethanone; phenylglyoxalic esters such as methyl phenylglyoxalate; benzophenones such as benzophenone, 2-hydroxybenzophenone, 3-hydroxybenzo- phenone, 4-hydroxybenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4- methylbenzophenone, 2,4-dimethylbenzophenone, 3,4-dimethylbenzophenone
  • the abovementioned photoinitiators are present in amounts of ⁇ 0.01% by weight based on the solids content of the paint formulation and are preferably not present at all.
  • the average particle size of the aqueous dispersions of urethane (meth)acrylates is in general in the range of from 20 to 140 nm, preferably of from 40 to 90 nm.
  • the aqueous dispersions of urethane (meth) acrylates in general have a particle size distribution that is characterized by a dw value within a range of from 10 to 70 nm, preferably of from 20 to 70 nm, or that is characterized by a dso value within a range of from 15 to 120 nm, preferably of from 35 to 90 nm, or that is characterized by a dgo value of from 30 to 220 nm, preferably of from 70 to 100 nm.
  • the particle size distribution of the aqueous dispersions of urethane (meth)acrylates is characterized by a d value of from 10 to 70 nm, a dso value of from 15 to 120 nm and a dgo value of from 30 to 220 nm.
  • dw is from 20 to 70 nm
  • dso is from 35 to 90 nm
  • dgo is from 70 to 100 nm.
  • the particle size distribution is determined by means of dynamic light scattering at 25°C using a Beckmann Coulter Delsa Nano S particle size analyser.
  • Suitable water-dispersible urethane (meth)acrylates are generally obtainable from components
  • the isocyanate component (a) is preferably selected from
  • (a2) polyisocyanates that are obtainable by oligomerization of a diisocyanate and have an average isocyanate functionality of at least 2.5, preferably a functionality within a range from 2.5 to 4, wherein the diisocyanate includes a saturated alicyclic structural unit,
  • (a3) polyisocyanates that are obtainable by oligomerization of a C2 to Cs alkylene diisocyanate and have an average isocyanate functionality of at least 2.5, preferably within a range from 2.5 to 6, and especially within a range from 2.8 to 4.0.
  • the diisocyanates (a1) are preferably saturated aliphatic and saturated alicyclic diisocyanates having 4 to 20 carbon atoms.
  • diisocyanates having 4 to 20 carbon atoms are aliphatic diisocyanates such as tetramethylene diisocyanate, pentamethylene 1 ,5-diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di(isocyanatocyclohexyl)methane, 1-
  • hexamethylene diisocyanate 1,3-bis(isocyanatomethyl)cyclo- hexane, isophorone diisocyanate, 4,4'-di(isocyanatocyclohexyl)methane, and 2,4'-di(isocyanato- cyclohexyl)methane and mixtures thereof, and very particular preference to isophorone diisocyanate, 4,4'-di(isocyanatocyclohexyl)methane, and hexamethylene diisocyanate.
  • the diisocyanate compounds (a1) are selected from saturated alicyclic diisocyanates and in particular from isophorone diisocyanate and bis(4-isocyanatocyclo- hexyl)methane and mixtures thereof.
  • the polyisocyanates (a2) are oligomers obtainable by oligomerization of diisocyanates having at least one, in particular just one, cycloaliphatic structural unit, e.g. 1 or 2 cyclohexane rings, and which have preferably 4 to 20 carbon atoms.
  • diisocyanates are also referred to hereinafter as cycloaliphatic diisocyanates.
  • cycloaliphatic diisocyanates are 1 ,4-, 1 ,3- or 1 ,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di(isocyanatocyclohexyl)methane, 1-isocyanato-3,3,5- trimethyl-5-(isocyanatomethyl)cyclohexane (isophorone diisocyanate), 1 ,3- or 1 ,4-bis(isocy- anatomethyl)cyclohexane or 2,4-, or 2, 6-diisocyanato-1 -methylcyclohexane and also 3(or 4),8(or 9)-bis(isocyanatomethyl)tricyclo[5.2.1.0 2 ’ 6 ]decane isomer mixtures.
  • Suitable oligomers (a2) are i. isocyanurates of the abovementioned cycloaliphatic diisocyanates, ii. polyisocyanates that have uretdione groups and are based on the abovementioned cycloaliphatic diisocyanates, iii. polyisocyanates that have biuret groups and are based on the abovementioned cycloaliphatic diisocyanates, iv. polyisocyanates that have urethane and/or allophanate groups and are based on the abovementioned cycloaliphatic diisocyanates, v.
  • polyisocyanates that have oxadiazinetrione groups and are based on the abovementioned cycloaliphatic diisocyanates, vi. polyisocyanates that have iminooxadiazinetrione groups and are based on the abovementioned cycloaliphatic diisocyanates.
  • Preferred polyisocyanate compounds (a2) are selected from isocyanurates of cycloaliphatic diisocyanates, for example isocyanurates of isophorone diisocyanate, of
  • Such oligomers (a2) typically have a number-average molecular weight within a range from 400 to 1800 daltons, in particular within a range from 500 to 1600 daltons.
  • the degree of oligomerization is typically within a range from 2.5 to 8, in particular within a range from 3 to 6.
  • the average isocyanate functionality of the oligomers (a2) is preferably within a range from 2.5 to 6 and in particular within a range from 2.8 to 4.5 and especially within a range from 2.8 to 4.0.
  • Average isocyanate functionality is understood as meaning the average number of isocyanate groups in the oligomer (number average).
  • oligomers (a2) having an isocyanate equivalent weight within a range from 180 to 500 g/mol NCO, in particular within a range from 200 to 400 g/mol NCO.
  • the diisocyanate content is preferably below 10% by weight based on oligomer (a2).
  • the polyisocyanate compounds (a2) are particularly preferably selected from isocyanurates of isophorone diisocyanate, in particular those having an average isocyanate functionality within a range from 2.5 to 6, in particular within a range from 2.8 to 4.5, and especially within a range from 2.8 to 4.0, and an isocyanate equivalent weight preferably within a range from 200 to 400 g/mol NCO.
  • the polyisocyanates (a3) are allophanates, isocyanurates, and uretdiones of a C2 to Cs alkylene diisocyanate, such as tetramethylene diisocyanate, 1 ,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1 ,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate.
  • a C2 to Cs alkylene diisocyanate such as tetramethylene diisocyanate, 1 ,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1 ,6-diisocyanatohexane), octamethylene diiso
  • Such oligomers (a3) typically have a number-average molecular weight within a range from 400 to 1600 daltons, in particular within a range from 450 to 1400 daltons.
  • the degree of oligomerization is typically within a range from 2.5 to 8, in particular within a range from 3 to 6.
  • oligomers (a3) having an isocyanate equivalent weight within a range from 120 to 400 g/mol NCO, in particular within a range from 150 to 300 g/mol NCO.
  • the diisocyanate content in oligomers (a3) is preferably below 10% by weight based on the total amount of oligomers (a3).
  • Preferred polyisocyanate compounds (a3) are selected from isocyanurates of a C4 to Cs alkylene diisocyanate, in particular isocyanurates of hexamethylene diisocyanate.
  • the polyisocyanate (a3) is particularly preferably selected from an isocyanurate of hexamethylene diisocyanate having an average isocyanate functionality within a range from 2.5 to 6, in particular within a range from 2.8 to 4.5, and especially within a range from 2.8 to 4.0, and preferably having an isocyanate equivalent weight within a range from 150 to 300 g/mol NCO.
  • the isocyanate component (a) essentially contains no isocyanate components different from the abovementioned isocyanates (a1), (a2), and (a3), i.e. the proportion of isocyanate compounds different from the abovementioned isocyanates typically does not exceed 5% by weight, in particular 1 % by weight, based on the total weight of isocyanate component (a).
  • Component (b) comprises at least one compound having at least one, in particular just one, eth- ylenically unsaturated double bond in the form of an acrylate or methacrylate group and also at least one, in particular just one, functional group F that reacts with an isocyanate group to form a covalent bond.
  • the functional group F is preferably selected from -OH, -NH2, and -NRH, where R is a saturated or unsaturated aliphatic hydrocarbon radical having 1 to 10 carbon atoms.
  • the functional group F is particularly preferably an -OH group.
  • Preferred components (b) are selected from hydroxy C2 to Cs alkyl esters of acrylic acid, hydroxy C2 to Cs alkyl esters of methacrylic acid, diesters of C3 to Cs alkanetriols with acrylic acid and diesters of C3 to Cs alkanetriols with methacrylic acid, component (b) being selected in particular from hydroxy C2 to C4 alkyl esters of acrylic acid.
  • Compound (b) is especially 2-hydroxy- ethyl acrylate.
  • Component (c) can be either (c1) nonionic low-molecular-weight diols or polyols having a molecular weight of ⁇ 350 g/mol or (c2) nonionic polymeric diols or polyols having a number-average molecular weight of > 350 g/mol.
  • Suitable as component (c1) are aliphatic and cycloaliphatic diols.
  • aliphatic diols are ethylene glycol, propane-1 , 2-diol, propane-1 , 3-diol, butane-1 ,2-diol, butane-1 ,3-diol, butane-1 ,4- diol, butane-2, 3-diol, pentane-1 , 2-diol, pentane-1 , 3-diol, pentane-1 ,4-diol, pentane-1 ,5-diol, pen- tane-2, 3-diol, pentane-2,4-diol, hexane-1 , 2-diol, hexane-1 , 3-diol, hexane-1 ,4-diol, hexane-1 , 5- diol, hexane-1 , 6-
  • cycloaliphatic diols examples include cyclopentane-1 , 2-diol and -1 , 3-diol, cyclohexane-1 , 2-diol, - 1 , 3-diol, and -1 ,4-diol, 1 ,1-, 1 ,2-, 1 ,3-, and 1 ,4-bis(hydroxymethyl)cyclohexanes, 1 ,1-, 1 ,2-, 1 ,3-, and 1 ,4-bis(hydroxyethyl)cyclohexanes, and bis(4-hydroxycyclohexane)isopropylidene.
  • cyclohexane-1 2-diol, -1 , 3-diol, and -1 ,4-diol
  • 1 ,3-bis(hydroxyme- thyl)cyclohexane 1 ,4-bis(hydroxymethyl)cyclohexane
  • bis(4-hydroxycyclohexyl)methane bis(4-hydroxycyclohexane)isopropylidene.
  • Suitable polymeric polyol components (c2) are polyesterols, polyetherols and polycarbonate polyols. So as to achieve a minimal tendency to yellowing, the polymeric polyol component (c2) preferably contains no aromatic groups.
  • the polymeric polyol component (c2) preferably has a number-average molecular weight within a range from 350 to 10 000 g/mol, in particular within a range from 400 to 8000 g/mol, especially within a range from 450 to 5000 g/mol.
  • the polymeric polyol component (c2) comprises at least one aliphatic polyester polyol.
  • Preferred polyesterols are those based on aliphatic or cycloaliphatic dicarboxylic acids with aliphatic diols.
  • Preferred polyester polyols have OH values, determined in accordance with DIN 53240-2:2007-11 , within a range from 5 to 220, in particular within a range from 10 to 200, mg KOH/g.
  • the acid value is preferably below 20 mg KOH/g, in particular below 10 mg KOH/g.
  • Suitable aliphatic diols for preparation of the polyester polyols have preferably 2 to 40 carbon atoms, in particular 4 to 10 carbon atoms.
  • Examples of aliphatic diols are ethylene glycol, pro- pane-1 , 2-diol, propane-1 , 3-diol, butane-1 , 2-diol, butane-1 ,3-diol, butane-1 ,4-diol, butane-2,3- diol, pentane-1 , 2-diol, pentane-1 , 3-diol, pentane-1 ,4-diol, pentane-1 ,5-diol, pentane-2, 3-diol, pentane-2,4-diol, hexane-1 , 2-diol, hexane-1 , 3-diol, hexane-1 ,4-diol, he
  • higher polyethylene glycols HO(CH2CH2O)n-H are also suitable.
  • higher polypropylene glycols HO(CH[CH3]CH2O)n-H where n is an integer and n > 4, e.g. 4 to 20, polyethylene polypropylene glycols, in particular those having 4 to 20 repeat units, wherein the sequence of the ethylene oxide and propylene oxide units may be blockwise or random, polytetramethylene glycols, in particular those having 4 to 20 repeat units, and polypropane-1 ,3-diols, in particular those having 4 to 20 repeat units.
  • Suitable cycloaliphatic diols for preparation of the polyester polyols are cyclopentane- 1 , 2-diol and -1 , 3-diol, cyclohexane-1 , 2-diol, -1 , 3-diol, and -1 ,4-diol, 1 ,1-, 1 ,2-, 1 ,3-, and 1 ,4-bis(hy- droxymethyl)cyclohexanes, 1 ,1-, 1 ,2-, 1 ,3-, and 1 ,4-bis(hydroxyethyl)cyclohexanes, bis(4-hy- droxycyclohexane)methane, and bis(4-hydroxycyclohexane)isopropylidene.
  • cyclohexane-1 2-diol, -1 , 3-diol, and -1 ,4-diol, 1 ,3-bis(hydroxymethyl)cyclohex- ane and 1 ,4-bis(hydroxymethyl)cyclohexane, and bis(4-hydroxycyclohexane)methane.
  • Preferred diols for preparation of the polyester polyols are acyclic aliphatic diols having 2 to 8 carbon atoms, for example ethylene glycol, propane-1 , 2-diol, propane-1 , 3-diol, 2,2-di- methylethane-1 , 2-diol, 2, 2-dimethylpropane-1 , 3-diol (neopentyl glycol), 2,2-diethylpropane-1 ,3- diol, 2-methyl-2-ethylpropane-1 , 3-diol, butane-1 , 2-diol, butane-1 , 3-diol, butane-1 , 4-diol, hexane-
  • diols for preparation of the polyester polyols are ethylene glycol, propane-1 , 2-diol, propane-1 , 3-diol, neopentyl glycol, butane-1 , 4-diol, and diethylene glycol.
  • the dicarboxylic acid structural units used for preparation of the polyester polyols may be the free acids or ester-forming derivatives thereof.
  • Derivatives are preferably understood as meaning the relevant anhydrides, monoalkyl esters, and dialkyl esters, preferably monoalkyl esters and di-Ci to C4 alkyl esters, particularly preferably monomethyl and dimethyl esters and the corresponding monoethyl and diethyl esters, also monovinyl and divinyl esters and also mixed esters for example having different Ci to C4 alkyl components, especially mixed methyl ethyl esters.
  • Ci to C4 alkyl means methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl, ethyl and n-butyl, more preferably methyl and ethyl, and most preferably methyl.
  • Suitable dicarboxylic acids that may be used for preparation of the polyester polyols are in particular aliphatic dicarboxylic acids/alkanedicarboxylic acids having 2 to 12 carbon atoms and cycloaliphatic dicarboxylic acids/cycloalkanedicarboxylic acids having 7 to 14 carbon atoms.
  • polyester polyols examples include oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane-a, co-dicarboxylic acid, do- decane-a, co-dicarboxylic acid, and derivatives thereof.
  • cycloaliphatic dicarboxylic acids are cis- and trans-cyclohexane-1 ,2-dicarboxylic acid (hexahydrophthalic acids), cis- and trans-cyclohexane-1 ,3-dicarboxylic acid, cis- and trans-cyclohexane-1 ,4-dicarboxylic acid, 1 ,2-, 1 ,3- or 1 ,4-cyclohex-4-enedicarboxylic acid (tetrahydrophthalic acids), cis- and trans-cyclopen- tane-1 ,2-dicarboxylic acid, cis- and trans-cyclopentane-1 ,3-dicarboxylic acid, and derivatives thereof.
  • Preferred dicarboxylic acids are saturated aliphatic dicarboxylic acids, in particular those having 3 to 10 carbon atoms such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane-a, co-dicarboxylic acid, and dodecane-a, co-dicarboxylic acid.
  • polyesterols are lactone-based polyesterols, in particular those based on an aliphatic lactone having 4 to 8 carbon atoms, for example butyrolactone, valerolactone or caprolactone.
  • Component (c2) is preferably selected from aliphatic polyesters, in particular from aliphatic polyester polyols formed from at least one C3 to C12 alkanedicarboxylic acid and at least one C3 to C10 alkanediol.
  • component (c2) is a polyester polyol that is formed from adipic acid and neopentyl glycol and in particular has an OH value within a range from 20 to 200 mg KOH/g.
  • the aliphatic polyester preferably has in this embodiment a number-average molecular weight within a range from 450 to 5000 g/mol.
  • the aliphatic polyester has in this embodiment a number-average molecular weight within a range from 480 to 2500 g/mol, more preferably within a range from 500 to 2000 g/mol.
  • Compounds (d) have at least one, e.g. one or two, ionic or ionizable groups I' and at least one, e.g. one or two, functional groups F’ that react with an isocyanate group to form a covalent bond.
  • the functional group F' is preferably selected from -OH, -NH2, and -NR'H, where R' is a saturated or unsaturated hydrocarbon radical having 1 to 10 carbon atoms.
  • R' is a saturated or unsaturated hydrocarbon radical having 1 to 10 carbon atoms.
  • the functional group F' is an OH group.
  • the ionic or ionizable group I' is preferably selected from acid groups in the acid or salt form, in particular from carboxyl groups.
  • acid groups are -COOH, -SO3H or -PO3H.
  • the acid groups may be in their anionic forms and accordingly have a counterion.
  • counterions are alkali metal and alkaline earth metal ions, e.g. Li + , Na + , K + , Cs + , Mg 2+ , Ca 2+ or Ba 2+ .
  • the counterion present is ammonium ions or quaternary ammonium ions derived from ammonia or amines, especially tertiary amines, for example ammonium, methylammonium, dimethylammonium, trimethylammonium, ethylammonium, diethylammonium, triethylammonium, tributylammonium, diisopropylethylammonium, benzyldimethylammonium, monoethanolammonium, diethanolammonium, triethanolammonium, hydroxyethyldimethylammonium, hydroxyethyldiethylammonium, monopropanolammonium, dipropanolammonium, tripropanolammonium, piperidinium, piperazinium, N,N'-dimethylpiperazinium, mor- pholinium, pyridinium, tetramethylammonium, triethylmethylammonium, trie
  • F' is as defined above and is in particular OH
  • I' is an ionic or ionizable group, in particular an acid group, and especially a carboxyl group;
  • R is a saturated aliphatic or alicyclic hydrocarbon radical having 2 to 20 carbon atoms.
  • Particularly preferred compounds (d) are selected from aliphatic dihydroxycarboxylic acids, in particular those having 3 to 10 carbon atoms and salts thereof.
  • aliphatic dihydroxycarboxylic acids are 2,3-dihydroxypropanoic acid, 2,2-dimethylolpropionic acid, 2,2-dime- thylolbutyric acid, and 2,2-dimethylolpentanoic acid, preference being given to 2,2-dime- thylolpropionic acid and dimethylolbutyric acid.
  • the further compounds (e) can be poly(C2 to C3 alkylene ether) compounds having an average OH functionality within a range from 0.9 to 1.2.
  • the poly(C2 to C3 alkylene ether) compounds generally have a number-average molecular weight within a range from 250 to 2500 g/mol.
  • Preferred compounds (e) are Ci- to C4-alkyl polyethylene glycols, in particular methyl polyethylene glycols, having a number-average molecular weight within a range from 250 to 2500 g/mol.
  • the paint formulation may comprise, as UV-curable paint constituents, low-molecular-weight poly(meth)acrylates of low-molecular-weight diols or polyols (low-molecular-weight diols or polyols being ones having a molecular weight of
  • low-molecular-weight poly(meth)acrylates (f) are dispersible in water (maximum water solubility 10 g/L) and have no isocyanate-reactive groups.
  • Preferred poly(meth)acry- lates (f) are selected from diacrylates of C2 to C10 alkanediols, triacrylates of C3 to C10 alkanetriols, tetraacrylates of C4 to C10 alkanetetraols, tetraacrylates of bis(dihydroxy-C3 to C10 alkyl) ethers, hexaacrylates of bis(trihydroxy-C4 to C10 alkyl) ethers, and the corresponding methacrylates.
  • Particularly preferred low-molecular-weight poly(meth)acrylates (f) are selected from dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, bis(dimethylolpropane) tetraacrylate, and bis(pentaerythritol) hexaacrylate.
  • the paint formulation comprises low-molecular- weight poly(meth)acrylates (f) of this type.
  • their content is generally 5% to 50% by weight, preferably 5% to 30% by weight, based on the sum of urethane (meth)acrylates and poly(meth)acrylates (f).
  • the paint formulation essentially comprises no further UV-curable paint constituents, i.e. at least 90% by weight, preferably at least 95% by weight, and especially 100% by weight, of the UV-curable paint constituents is urethane (meth)acrylates and poly(meth)acrylates (f).
  • the paint formulation does not comprise any low-molec- ular-weight poly(meth)acrylates (f).
  • at least 90% by weight, preferably at least 95% by weight, and in particular 100% by weight, of the UV-curable paint constituents is urethane (meth) acrylates.
  • the paint formulations may comprise further auxiliaries and additives customary in coatings, such as leveling agents, defoamers, UV absorbers, dyes, pigments, matting agents and/or fillers.
  • the water-based paint formulation is a clearcoat formulation and only curing step (iii) is carried out.
  • the clearcoat formulations preferably comprise no photoinitiators at all.
  • the water-based paint formulation is a pigmented paint formulation and curing steps (iii) and (iv) are carried out.
  • the paint formulation comprises at least one photoinitiator activatable through UV radiation having a wavelength of > 350 nm.
  • Curing step (iv) can be carried out by irradiating with UV LEDs in the 350 nm to 420 nm range, for example at 365 nm, 385 nm, 395 nm or 405 nm, or with a gas-discharge lamp, for example an undoped mercury lamp or with a doped mercury lamp having gallium or indium doping, iron doping or lead doping or having another suitable doping.
  • a gas-discharge lamp for example an undoped mercury lamp or with a doped mercury lamp having gallium or indium doping, iron doping or lead doping or having another suitable doping.
  • UV LEDs in a particularly preferred embodiment with UV LEDs at 365 nm.
  • Photoinitiators activatable by UV radiation having a wavelength of > 350 nm generally have an absorption band with a maximum in the 360 to 420 nm range.
  • These include in particular acylphosphine oxides such as (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, [ethoxy(phe- nyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone, and bis(2,4,6-trimethylbenzoyl)phe- nylphosphine oxide, also bisacylphosphine oxides and acylphosphine sulfides. Clearcoats of the invention do not comprise these photoinitiators.
  • the pigments may be inorganic pigments, for example aluminum oxide, iron pigments such as iron(lll) oxide, chromium(lll) oxide, titanium(IV) oxide, zirconium(IV) oxide, zinc oxide, zinc sulfide, zinc phosphate, mixed metal oxide phosphates, molybdenum sulfide, cadmium sulfide, graphite, vanadates such as bismuth vanadate, chromates such as lead(IV) chromates, molybdates such as lead(IV) molybdate, and mixtures thereof, or organic pigments.
  • inorganic pigments for example aluminum oxide, iron pigments such as iron(lll) oxide, chromium(lll) oxide, titanium(IV) oxide, zirconium(IV) oxide, zinc oxide, zinc sulfide, zinc phosphate, mixed metal oxide phosphates, molybdenum sulfide, cadmium sulfide, graphite, vana
  • organic pigments examples include color pigments and pearlescent pigments such as azo pigments, disazo pigments, naphthol pigments, benzimidazolone pigments, azo condensation pigments, metal complex pigments, isoindolinone pigments, quinoph- thalone pigments and dioxazine pigments, polycyclic pigments such as indigo, thioindigo, quina- cridone, phthalocyanines, perylenes, perinones, anthraquinones, for example aminoanthraquinones or hydroxyanthraquinones, anthrapyrimidines, indanthrones, flavanthrones, py- ranthrones, anthanthrones, isoviolanthrones, diketopyrrolopyrroles and also carbazoles, for example carbazole violet, and the like.
  • azo pigments examples include azo pigments, disazo pigments, naphthol pigments, benzimidazolone pigments, azo condensation pigment
  • organic pigments can be found in the following monograph: W. Herbst, K. Hunger “Industrielle Organische Pigmente” [Industrial organic pigments], 2nd edition, 1995, VCH Verlagsgesellschaft, ISBN: 3-527-28744-2.
  • Suitable fillers and matting agents include silicates, for example silicates obtainable by hydrolysis of silicon tetrachloride such as Aerosil® from Degussa, siliceous earth, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc. Matting agents are in particular untreated or treated silicas, in particular precipitated and fumed silicas, for example Acematt® types 3300, 3600, OK 412, OK500, OK607, and TS100 from Evonik Industries.
  • silicates for example silicates obtainable by hydrolysis of silicon tetrachloride such as Aerosil® from Degussa, siliceous earth, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc. Matting agents are in particular untreated or treated silicas, in particular precipitated and fumed silicas, for example Acematt® types 3300, 3600, OK 412, OK500, OK607, and TS100 from Evonik Industries.
  • Suitable stabilizers include typical UV absorbers such as oxanilides, triazines, and benzotriazole (the latter obtainable as Tinuvin® products from BASF SE) and benzophenones. These may be used alone or together with suitable free-radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, for example bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate. Stabilizers are typically used in amounts of 0.1% to 5.0% by weight based on the “solid” components present in the preparation.
  • suitable free-radical scavengers for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, for example bis(2,2,6,6-tetramethyl-4-piperidyl) sebac
  • the paint formulation is a pigment-containing paint formulation that, in addition to the polyurethane (meth)acrylate, comprises a pigment, preferably at least one inorganic pigment.
  • the pigment content is here preferably within a range from 1% to 50% by weight based on the composition.
  • the mass ratio of pigment to polyurethane (meth)acrylate is preferably within a range from 1 :20 to 1:1 and in particular within a range from 1 :10 to 1 :5.
  • the aqueous paint formulations are preferably paint formulations for the coating of wood, paper, textile, leather, nonwoven, plastics surfaces, glass, ceramic, mineral building materials, such as cement moldings and fiber-cement panels, and of coated or uncoated metals.
  • aqueous paint formulation to the substrate to be coated may be carried out in a known manner, by spraying, troweling, knifecoating, brushing, rolling, roller coating or pouring. It is likewise possible to apply the paint formulations to a substrate by means of a printing process such as offset printing, flexographic printing, intaglio printing, screen printing or inkjet printing, or by means of a similar method.
  • the coverage is generally within a range from 1 to 250 g/m 2 , preferably within a range from 10 to 150 g/m 2 , and more preferably within a range from 25 to 125 g/m 2 , based on the solids content of the aqueous paint formulation.
  • the amount applied it is also possible for the amount applied to be ⁇ 1 g/m 2 .
  • the aqueous paint formulations are in particular paint formulations for the coating of metals, plastics surfaces such as PVC or melamine, cement or concrete surfaces, for example of concrete roof tiles and fiber cement panels, and also for the coating of wood and woodbase materials, and also of paper, for example furniture decals.
  • the aqueous paint formulations and the method of the invention are suitable in particular for the coating of wood and woodbase materials and wood-containing substrates, such as fiberboard, and also for the coating of substrates containing cellulose fibers, for example paper, paperboard or cardboard.
  • Wood substrates can for example be pure-wood substrates, for example oak, spruce, pine, beech, maple, walnut, makore, chestnut, plane, robinia, ash, birch, pine, and elm, pure-wood woodbase materials, such as cross-laminated timber, block plywood, glued laminated timber or similar, laminated plywood, veneer wood materials such as veneer plywood, laminated veneer lumber, veneer strip lumber, flexible plywood, or else chipboard materials such as MDF panels, HDF panels or OSB panels, and also cork.
  • pure-wood substrates for example oak, spruce, pine, beech, maple, walnut, makore, chestnut, plane, robinia, ash, birch, pine, and elm
  • pure-wood woodbase materials such as cross-laminated timber, block plywood, glued laminated timber or similar, laminated plywood, veneer wood materials such as veneer plywood, laminated veneer lumber, veneer strip lumber, flexible plywood, or else chipboard materials such as MDF panels, HD
  • Scotch-Brite SLIFN nonwoven 500 g weight
  • the Scotch-Brite SLIFN nonwoven is used to scratch across the paint surface with the appropriate weight. 20 double strokes (movement back and forth) are executed and the gloss of the coating before and after scratching is determined at a 60° measurement angle.
  • the chemical resistance was determined on cured films on white MDF panels.
  • the chemical resistance toward various substances was determined by the IKEA R2 method. 24 h water
  • Lamp IIV-C lamp from 1ST Metz GmbH with special glass for high transmissions up to 250 nm, UVC-optimized through appropriate current/voltage parameters
  • IIV-C dose 1150 mJ/cm 2
  • IIV-C dose 1150 mJ/cm 2 combined with 22 W 365 nm LED
  • the paint formulations comprised a photoinitiator (Omnirad 184 in the clearcoats and additionally Omnirad 819 DW in the pigmented paints).
  • the clearcoat formulations did not comprise a photoinitiator and the pigmented paint formulations comprised solely Omnirad 819 DW (deep-curing initiator) for deep curing with the additional LED light source.
  • Laromer UA 9135 Aqua is a UV-curable, water-based PU dispersion comprising the reaction product from HDI, IPDI, polyesterol from adipic acid and neopentyl glycol, polyetherol, dimethylolpropionic acid, and 2-hydroxyacrylate and also low-molecular-weight poly(meth)acrylates based on TMP, glycerol, pentaerythritol, and ethoxylates or propoxylates thereof.
  • the pigmented formulations according to example 2 were cured under the same conditions. Unlike with the clearcoat according to example 1 , a medium-pressure Ga lamp was additionally used for deep curing of the pigmented paint film (Table 3).
  • the new vacuum IIV-C lamp from 1ST Metz GmbH was used without an inert gas atmosphere.
  • the spectral output of the new 1ST lamp at a power consumption of 240 W/cm is shown below:
  • the clearcoat formulation cured with the new IIV-C lamp does not comprise a photoinitiator (Ta- ble 4).
  • the cured clearcoat film exhibited properties (Table 6) comparable to those of the standard-cured clearcoat film comprising a photoinitiator (example 1).
  • Table 6 Properties of the clearcoat cured according to the method of the invention (UV- C-optimized medium-pressure Hg lamp from 1ST Metz GmbH)
  • Pigmented paint formulations corresponding to examples 5 and 6 were produced without a surface initiator (Omnirad 184), using only the deep-curing initiator Omnirad 819 DW (Table 7). Curing was effected using the UV-C-optimized medium-pressure Hg lamp from 1ST for surface curing in combination with a 22 W 365 nm LED lamp for deep curing (belt speed 10 m/min).
  • Table 7 Pigmented paint formulation for curing experiments in accordance with the invention for 100 g paint with only a deep-curing photoinitiator (Omnirad 819 DW) 100
  • Table 8 Properties of the pigmented paint cured according to the method of the invention (UV-C-optimized medium-pressure Hg lamp from 1ST Metz GmbH in combination with 22 W 365 nm LED lamp)

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un procédé de production d'un revêtement de peinture sur un substrat par séchage UV d'une formulation de peinture à base d'eau comprenant une dispersion aqueuse de (méth)acrylates d'uréthane, ledit procédé comprenant les étapes dans la séquence (i) à (iv) : (i) l'application de la formulation de peinture comprenant la dispersion aqueuse de (méth)acrylates d'uréthane sur le substrat ; (ii) le séchage de la formulation de peinture ; (iii) le séchage de la formulation de peinture séchée par irradiation au moyen d'un rayonnement UV-C dans la plage de longueurs d'onde de 180 à 280 nm, ce qui permet d'obtenir un film de peinture au moins partiellement séché ; (iv) l'irradiation facultative du film de peinture au moins partiellement séché au moyen d'un rayonnement UV présentant une longueur d'onde supérieure ou égale à 350 nm aux fins d'un séchage ultérieur du film de peinture ; la teneur totale dans la formulation de peinture de photo-initiateurs pouvant être activés par un rayonnement UV présentant une longueur d'onde inférieure à 350 nm étant inférieure à 0,01 % en poids sur la base de la teneur en solides de la formulation de peinture.
EP21766434.1A 2020-08-28 2021-08-19 Procédé de séchage uv de dispersions de peinture de polyuréthane à base d'eau sans initiateurs de surface pouvant être activés par uv-c Pending EP4204462A1 (fr)

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NL8401785A (nl) * 1984-06-04 1986-01-02 Polyvinyl Chemie Holland Werkwijze voor de bereiding van een waterige dispersie van urethan-acrylaat entcopolymeren, alsmede aldus verkregen stabiele waterige dispersie.
DE19949383A1 (de) 1999-10-13 2001-04-19 Basf Ag Verfahren zur Herstellung von Beschichtungen durch UV-Härtung
KR101351189B1 (ko) * 2012-06-28 2014-01-15 조광페인트주식회사 데코시트용 도료 조성물 및 데코시트 제조방법
JP2018530639A (ja) * 2015-08-17 2018-10-18 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ポリウレタン（メタ）アクリレートを含む水性ポリマー組成物
EP3668656B1 (fr) * 2017-08-16 2024-07-24 Basf Se Procédé de production de revêtements mats sur des substrats plats

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