EP1805242A1 - Resines aqueuses durcissables par rayonnement, procede de fabrication et utilisation - Google Patents

Resines aqueuses durcissables par rayonnement, procede de fabrication et utilisation

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Publication number
EP1805242A1
EP1805242A1 EP05777794A EP05777794A EP1805242A1 EP 1805242 A1 EP1805242 A1 EP 1805242A1 EP 05777794 A EP05777794 A EP 05777794A EP 05777794 A EP05777794 A EP 05777794A EP 1805242 A1 EP1805242 A1 EP 1805242A1
Authority
EP
European Patent Office
Prior art keywords
radiation
aqueous
component
curable resin
aldehyde
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05777794A
Other languages
German (de)
English (en)
Inventor
Patrick GLÖCKNER
Lutz Mindach
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.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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Filing date
Publication date
Application filed by Degussa GmbH filed Critical Degussa GmbH
Publication of EP1805242A1 publication Critical patent/EP1805242A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/02—Condensation polymers of aldehydes or ketones only
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C09D161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea

Definitions

  • Aqueous, radiation-curable resins a process for their preparation and their use
  • the invention relates to aqueous, radiation-curable resins, a process for their preparation and their use in adhesives and coating materials.
  • VOC volatile organic compounds
  • the film-forming components are relatively low molecular weight in the coating material and therefore low viscosity, so that can be dispensed with high proportions of organic solvents.
  • Permanent coatings are obtained by forming a high molecular weight, polymeric network is formed by application of the coating material by z. B. electron beam or UV light initiated crosslinking reactions.
  • the viscosity is often so high that z. B. a spray application can not be done.
  • the problem of high viscosity is overcome by the use of radiation-curable polymers which have been dispersed in water, since then the processing viscosity is independent of the molecular weight of the polymer (K. Buysens, M. Tielemans, T. Randoux, Surface Coatings International Part A, 5 (2003), 179-186).
  • Ketone aldehyde resins are used in coating materials, for. B. used as additive resins to improve certain properties such as drying speed, gloss, hardness or scratch resistance.
  • ketone-aldehyde resins have hydroxy groups and can therefore only with z.
  • polyisocyanates or amine resins are crosslinked. These crosslinking reactions are usually initiated or accelerated thermally.
  • the ketone-aldehyde resins are not suitable. Therefore, the ketone-aldehyde resins are commonly used in radiation-curable coating material systems z. B. used as a film-forming, but not crosslinking additional component. Such coatings are often due to the uncrosslinked shares low resistance to z. As gasoline, chemicals or solvents.
  • EP 902 065 describes the use of non-radiation-curable resins of urea (derivatives), ketones or aldehydes as an additional component in admixture with radiation-curable resins.
  • No. 4,070,500 describes the use of nonradiation curable ketone-formaldehyde resins as a film-forming component in radiation-curable inks.
  • DE 34 06 473 and DE 34 06 474 or EP 154 835 describe aqueous dispersions of urea-aldehyde resins, ketone resins or ketone-aldehyde resins using organic protective colloids.
  • protective colloids can adversely affect properties such as corrosion resistance in the subsequent application, these resins are not crosslinkable by radiation.
  • EP 594 038 likewise describes radiation-curable, aqueous urea-formaldehyde resins.
  • the object of the present invention was to modify hydroxyl-containing ketone, ketone-aldehyde, urea-aldehyde and phenolic resins and their hydrogenated secondary products chemically hydrophilic so that they are dispersible or soluble in water and by radiation in the presence of a suitable additive in a polymeric network can be converted.
  • a process for their preparation should be found.
  • the aqueous resin dispersions should be stable to hydrolysis and storage.
  • this object has been achieved by reacting hydroxyl-containing ketone, ketone-aldehyde, urea-aldehyde and phenolic resins and the hydrogenated derivatives with polycarboxylic acids and / or hydrophilic modified (poly) isocyanates and a component containing at least one ethylenically unsaturated group and has at least one reactive with respect to the resins grouping simultaneously.
  • ketone, ketone-aldehyde, urea-aldehyde and phenolic resins and their hydrogenated derivatives give stable aqueous dispersions which in the presence of an additive such.
  • a photoinitiator may optionally be converted in the presence of a photosensitizer by radiation in polymeric networks.
  • the aqueous systems of the invention are stable to hydrolysis and storage and contain no interfering additives z. B. in the form of emulsifiers or protective colloids.
  • the invention relates to aqueous, radiation-curable resin dispersions, essentially comprising the reaction product
  • the subject matter also relates to aqueous, radiation-curable resin dispersions obtained by polymer-analogous reaction of
  • Suitable ketones for the preparation of the ketone and ketone-aldehyde resins are all ketones, in particular acetone, acetophenone, methyl ethyl ketone, heptanone-2, pentanone-3, methyl isobutyl ketone, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexanone and any alkyl-substituted cyclohexanones having one or more alkyl radicals having a total of from 1 to 8 carbon atoms, individually or in admixture.
  • alkyl-substituted cyclohexanones 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert. Butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.
  • ketones usually all C-H-acidic ketones, can be used.
  • ketone-aldehyde resins based on the ketones acetophenone, cyclohexanone, 4-tert. Butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in mixture.
  • aldehyde component of the ketone-aldehyde resins are in principle unsubstituted or branched aldehydes, such as.
  • formaldehyde acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde and dodecanal.
  • all aldehydes mentioned in the literature as suitable for ketone resin syntheses can be used.
  • formaldehyde is used alone or in mixtures.
  • the required formaldehyde is usually used as about 20 to 40 wt .-% aqueous or alcoholic (eg, methanol or butanol) solution.
  • alcoholic eg, methanol or butanol
  • Other uses of formaldehyde such.
  • para-formaldehyde or trioxane are also possible.
  • Aromatic aldehydes, such as. B. benzaldehyde may also be included in admixture with formaldehyde.
  • Particularly preferred starting compounds for ketone-aldehyde resins (component A)) acetophenone, cyclohexanone, 4-tert. Butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone used alone or in mixture and formaldehyde.
  • component A is also urea-aldehyde resins using a urea of the general formula (i)
  • R 1 and R 2 are hydrocarbon radicals (for example alkyl, aryl and / or alkylaryl radicals) in each case having up to 20 carbon atoms and / or formaldehyde is used.
  • Suitable aldehydes of the general formula (ii) are, for example, isobutyraldehyde, 2-methylpentanal, 2-ethylhexanal and 2-phenylpropanal, and mixtures thereof. Isobutyraldehyde is preferred.
  • Formaldehyde may be in aqueous form, some or all of alcohols such. As methanol or ethanol may be used as paraformaldehyde and / or trioxane. In general, all monomers described in the literature for the preparation of aldehyde-urea resins are suitable.
  • compositions are for. B. in DE 27 57 220, DE-OS 27 57 176 and EP 271 776 described.
  • Suitable ketones for the preparation of the carbonyl-hydrogenated ketone-aldehyde resins are all ketones, in particular acetone, acetophenone, methyl ethyl ketone, heptanone-2, pentanone-3, methyl isobutyl ketone, cyclopentanone, cyclododecanone, mixtures of 2,2,4- and 2 , 4,4-trimethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals having a total of 1 to 8 carbon atoms, individually or in mixture.
  • alkyl-substituted cyclohexanones mention may be made of 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.
  • ketones usually all C-H-acidic ketones, can be used.
  • Carbonyl-hydrogenated ketone-aldehyde resins based on the ketones acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in a mixture are preferred.
  • aldehyde component of the carbonyl-hydrogenated ketone-aldehyde resins are in principle unsubstituted or branched aldehydes, such as.
  • formaldehyde acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde and dodecanal.
  • all aldehydes mentioned in the literature as suitable for ketone resin syntheses can be used.
  • formaldehyde is used alone or in mixtures.
  • the required formaldehyde is usually used as about 20 to 40 wt .-% aqueous or alcoholic (eg, methanol or butanol) solution.
  • alcoholic eg, methanol or butanol
  • Other uses of formaldehyde such.
  • para-formaldehyde or trioxane also possible.
  • Aromatic aldehydes, such as. B. benzaldehyde may also be included in admixture with formaldehyde.
  • Particularly preferred starting compounds for component A) are carbonyl-hydrogenated resins of acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in mixture and formaldehyde.
  • the resins of ketone and aldehyde are hydrogenated in the presence of a catalyst with hydrogen at pressures of up to 300 bar. In this case, part of the carbonyl groups of the ketone-aldehyde resin is converted into secondary hydroxyl groups.
  • B. hydrogen pressure, solvents, temperature may also contain other groups such.
  • component A) are also ring-hydrogenated phenol-aldehyde resins of the novolak type using the aldehydes such.
  • aldehydes such as formaldehyde, butyraldehyde or benzaldehyde, preferably formaldehyde used.
  • formaldehyde butyraldehyde or benzaldehyde, preferably formaldehyde used.
  • non-hydrogenated novolaks can be used, but then have lower light fastness.
  • ring-hydrogenated resins based on alkyl-substituted phenols.
  • all phenols mentioned as suitable in the literature for phenolic resin syntheses can be used.
  • Suitable phenols are phenol, 2- and 4-tert-butylphenol, 4-amylphenol, nonylphenol, 2-, and 4-tert-octylphenol, dodecylphenol, cresol, xylenols and bisphenols. They can be used alone or in mixture.
  • ring-hydrogenated, alkyl-substituted phenol-formaldehyde resins of the novolak type Preferred phenolic resins are reaction products of formaldehyde and 2- and 4-tert-butylphenol, 4-amylphenol, nonylphenol, 2-, and 4-tert-octylphenol and dodecylphenol.
  • the hydroxyl groups can also be hydrogenated, so that cycloaliphatic rings are formed.
  • the ring-hydrogenated resins have OH numbers of 50 to 450 mg KOH / g, preferably 75 to 350 mg KOH / g, more preferably from 100 to 300 mg KOH / g.
  • the proportion of aromatic groups is below 50 wt .-%, preferably below 30 wt .-%, more preferably below 10 wt .-%.
  • the hydrophilic modification takes place for.
  • Example by reacting the hydroxy-functional resin A) with a (poly) isocyanate and / or mixtures of different (poly) isocyanates with compounds which in addition to the hydrophilic or potentially hydrophilic group - d. H. those groups which become hydrophilic only after neutralization - at least one isocyanate-reactive function such as. B. hydroxy or amino groups.
  • Examples of such compounds for the hydrophilic modification of (poly) isocyanates are amino acids, hydroxy sulfonic acids, aminosulfonic acids and hydroxy carboxylic acids. Preference is given to using dimethylolpropionic acid and / or 2 - [(2-aminoethyl) amino] ethane sulfonic acid or derivatives thereof (component B)).
  • the hydrophilic modification can also be done with non-ionic groups or already neutralized compounds.
  • Suitable polyisocyanates for the preparation of B) are preferably di- to tetrafunctional polyisocyanates. Examples of these are cyclohexane diisocyanate, methylcyclohexane diisocyanate,
  • TIN 4-isocyanatomethyl-1, 8-octane diisocyanate
  • decane and triisocyanate undecanediol and triisocyanate
  • dodecane diisocyanates and triisocyanates isophorone diisocyanate (IPDI)
  • polyisocyanates are the compounds prepared by trimerization, allophanatization, biuretization and / or urethanization of simple diisocyanates having more than two isocyanate groups per molecule, for example the reaction products of these simple diisocyanates, such as IPDI, HDI and / or HMDI with polyhydric alcohols (For example, glycerol, trimethylolpropane, pentaerythritol) or polyvalent polyamines or triisocyanurates obtainable by trimerization of simple diisocyanates, such as IPDI, HDI and H 12 MDI.
  • polyhydric alcohols for example, glycerol, trimethylolpropane, pentaerythritol
  • polyvalent polyamines or triisocyanurates obtainable by trimerization of simple diisocyanates, such as IPDI, HDI and H 12 MDI.
  • component B polycarboxylic acids, polycarboxylic acid anhydrides, polycarboxylic acid esters and / or polycarboxylic acid halides, with a certain amount of acid groups being retained.
  • component C) are suitable maleic anhydride, (meth) acrylic acid derivatives such.
  • radiation-curable resins can be obtained by reacting component A) with B) and with isocyanates having an ethylenically unsaturated group, such as. B.
  • alkyl spacers having one to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms, such as.
  • methacrylethyl isocyanate methacrylic butyl isocyanate.
  • reaction products of hydroxyalkyl (meth) acrylates, whose Alkyl spacers have one to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms, and diisocyanates such.
  • HDI hexamethylene diisocyanate
  • MPDI 1,5-diisocyanato-2-methylpentane
  • reaction products in the molar ratio of 1: 1 of hydroxyethyl acrylate and / or hydroxyethyl methacrylate with isophorone diisocyanate and / or H 12 MDI and / or HDI.
  • polyisocyanates are the compounds prepared by trimerization, allophanatization, biuretization and / or urethanization of simple diisocyanates having more than two isocyanate groups per molecule, for example the reaction products of these simple diisocyanates, such as IPDI, HDI and / or HMDI with polyhydric alcohols (For example, glycerol, trimethylolpropane, pentaerythritol) or polyvalent polyamines or triisocyanurates obtainable by trimerization of simple diisocyanates, such as IPDI, HDI and H 12 MDI.
  • polyhydric alcohols for example, glycerol, trimethylolpropane, pentaerythritol
  • polyvalent polyamines or triisocyanurates obtainable by trimerization of simple diisocyanates, such as IPDI, HDI and H 12 MDI.
  • component A) it is also possible to use a part of component A) by further hydroxy-functional polymers such.
  • hydroxy-functional polyethers polyesters, polyurethanes and / or polyacrylates to replace.
  • mixtures of these polymers with components A) can be reacted directly with components B) and C) in a polymer-analogous manner. It has been shown that initially adducts of A) with z.
  • hydroxy-functional polyethers polyesters, polyurethanes and / or polyacrylates can be prepared using said di- and / or triisocyanates, which then only with the components B) and C) are reacted polymer analog.
  • the other hydroxy-functional polymers In contrast to the "pure" resins according to the invention, properties such as flexibility and hardness can be adjusted even better, the other hydroxy-functional polymers generally have molecular weights Mn between 200 and 10,000 g / mol, preferably between 300 and 5 000 g / mol.
  • the invention also provides a process for the preparation of aqueous, radiation-curable resin dispersions obtained by polymer-analogous reaction of
  • the resins according to the invention are prepared in the melt or in solution of a suitable organic solvent which, if desired, can be separated off by distillation after the preparation.
  • Suitable auxiliary solvents are low-boiling inert solvents which do not form a miscibility gap with water over wide ranges, have a boiling point at atmospheric pressure below 100 ° C. and, if desired, can be easily distilled to a residual content of less than 2% by weight and in particular of less than 0.5% by weight, based on the final dispersion or aqueous solution, and that it can be reused.
  • Suitable solvents of this type are for. As acetone, methyl ethyl ketone or tetrahydro-uranium. Basically suitable are also higher-boiling solvents such.
  • n-butyl glycol di-n-butyl glycol and N-methylpyrrolidone, which then remain in the dispersion.
  • reactive diluents can be used, ie, compounds which have a relatively low viscosity and can simultaneously undergo radiation-initiated crosslinking reactions. These compounds also remain in the later aqueous dispersion.
  • a solution or melt of the hydroxyl-containing ketone, ketone-aldehyde, urea-aldehyde, phenolic resins or their hydrogenated derivatives A) is the compound which contains at least one ethylenically unsaturated group and at least one opposite to A) or / and B) has reactive moiety (component C)), optionally in the presence of a suitable catalyst.
  • an adduct of 2 moles of diisocyanate and 1 mole of dimethylolpropionic acid and / or 2 - [(2-aminoethyl) amino] ethanesulfonic acid or derivatives thereof may optionally be prepared using a suitable solvent and a suitable catalyst.
  • the temperature of the reaction is selected. Temperatures between 30 and 245.degree. C., preferably between 50 and 140.degree. C., have proven successful in all reaction steps.
  • a suitable catalyst for the preparation of the resins of the invention can be used. Suitable are all known in the literature compounds that accelerate an OH-NCO reaction, such as. B. diazabicyclooctane (DABCO) and / or metal compounds such. B. dibutyltin dilaurate (DBTL).
  • DABCO diazabicyclooctane
  • DBTL dibutyltin dilaurate
  • the reaction can be stopped by adding an amine or alcohol. Depending on the nature of this component can be further properties such. B. the compatibility with other raw materials, eg. As pigments vary.
  • the neutralization of the potentially hydrophilic groups of the resins according to the invention can be carried out with inorganic and / or organic bases, such as.
  • inorganic and / or organic bases such as.
  • ammonia or organic amines Preferably used are primary, secondary and / or tertiary amines, such as. For example, ethylamine, propylamine, dimethylamine, dibutylamine, cyclohexylamine, benzylamine, morpholine, piperidine and triethanolamine.
  • volatile, tertiary amines in particular dimethylethanolamine, diethylethanolamine, 2-dimethylamino-2-methyl-1-propanol, triethylamine, tripropylamine and tributylamine in the case of anionic potential groups.
  • cationic potential ionic groups can be neutralized with inorganic and / or organic acids, such as. As acetic acid, formic acid, phosphoric acid, hydrochloric acid, etc.
  • the degree of neutralization depends on the content of neutralizable groups in the hydrophilically modified resin and is preferably 50 to 130% of the neutralization amount necessary for a stoichiometric neutralization.
  • reaction product of A), B) and C) may optionally be combined with other hydrophilic and / or non-hydrophilic resins and / or further components and then dispersed together, for example with acrylated polyesters, polyacrylates, polyesterurethanes, epoxyacrylates and / or polyether acrylates and alkyd resins, ketone-formaldehyde resins, ketone resins and / or unsaturated polyesters.
  • the solvent optionally present can be separated off after the reaction has ended, in which case a solution until dispersion of the product according to the invention in water is generally obtained.
  • aqueous dispersions according to the invention are suitable as the main component, base component or additional component in aqueous radiation-curing coating materials, adhesives, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealing and insulating materials, since they are characterized by fast drying and through-drying speeds , high blocking resistance due to their high glass transition temperature as well as very good pigment wetting properties even with hard-to-wet organic pigments.
  • these resins can be converted by irradiation into polymeric, insoluble networks which, depending on the content of ethylenically unsaturated groups, give elastomers to thermosets.
  • aqueous radiation-curing coating materials adhesives, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealing and insulating materials;
  • main component As the main component, base component or additive component in aqueous radiation-curing fillers, primers, fillers, basecoats, topcoats and clearcoats;
  • main component base component or additive component in aqueous radiation-curing coating materials, adhesives, printing inks and inks, polishes,
  • aqueous radiation-curing coating materials adhesives, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealing and
  • auxiliaries and additives selected from inhibitors, organic solvents which optionally contain unsaturated groups, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for influencing theological properties such.
  • auxiliaries and additives selected from inhibitors, organic solvents which optionally contain unsaturated groups, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for influencing theological properties such.
  • auxiliaries and additives selected from inhibitors, organic solvents which optionally contain unsaturated groups, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for influencing theological properties such.
  • B. thixotropic agents and / or thickening agents selected from inhibitors, organic solvents which optional
  • Leveling agents anti-skinning agents, defoamers, plasticizers, antistatic agents, lubricants, wetting and dispersing agents, preservatives such.
  • fungicides and / or biocides thermoplastic additives, dyes, pigments, matting agents, fire protection equipment, internal release agents, fillers and / or blowing agents.
  • coated articles made with compositions containing the dispersions of the invention.
  • the dispersion is provided with a polyurethane dispersion in the ratio 1: 1, applied to a glass plate or a Bonderblech and the solvent at elevated temperature (30 min, 80 ° C) evaporated. Subsequently, the films are cured by UV light (medium pressure mercury lamp, 7O W / optical filter 350 nm) for about 12 sec. Long.
  • UV light medium pressure mercury lamp, 7O W / optical filter 350 nm
  • the films are resistant to super-gasoline and methyl ethyl ketone.
  • Adhesion to steel sheet (DIN 53151): 0 Buchholz indentation hardness (DIN 53153): 83 Erichsen indentation (DIN 53156):> 9.5 mm King pendulum hardness (DIN 53157): 123 s

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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)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des résines aqueuses durcissables par rayonnement, un procédé de fabrication de ces résines et leur utilisation.
EP05777794A 2004-10-19 2005-08-23 Resines aqueuses durcissables par rayonnement, procede de fabrication et utilisation Withdrawn EP1805242A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004050775A DE102004050775A1 (de) 2004-10-19 2004-10-19 Wässrige, strahlenhärtbare Harze, ein Verfahren zu ihrer Herstellung und ihre Verwendung
PCT/EP2005/054134 WO2006042769A1 (fr) 2004-10-19 2005-08-23 Resines aqueuses durcissables par rayonnement, procede de fabrication et utilisation

Publications (1)

Publication Number Publication Date
EP1805242A1 true EP1805242A1 (fr) 2007-07-11

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EP05777794A Withdrawn EP1805242A1 (fr) 2004-10-19 2005-08-23 Resines aqueuses durcissables par rayonnement, procede de fabrication et utilisation

Country Status (10)

Country Link
US (1) US20080262144A1 (fr)
EP (1) EP1805242A1 (fr)
JP (1) JP2008517125A (fr)
KR (1) KR20070067148A (fr)
CN (1) CN1878812A (fr)
BR (1) BRPI0518215A (fr)
CA (1) CA2584389A1 (fr)
DE (1) DE102004050775A1 (fr)
TN (1) TNSN07143A1 (fr)
WO (1) WO2006042769A1 (fr)

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KR100933041B1 (ko) * 2007-10-15 2009-12-21 주식회사 태평양산업 방수투습 원단과 그 제조방법
US9144796B1 (en) 2009-04-01 2015-09-29 Johnson Matthey Public Limited Company Method of applying washcoat to monolithic substrate
ITMI20101492A1 (it) * 2010-08-04 2012-02-05 Claudio Martinuzzi Composizione per il rivestimento di utensili per lavorazione meccanica o stampi rotazionali e metodo per il suo impiego
EP2557094A1 (fr) * 2011-08-09 2013-02-13 Cytec Surface Specialties, S.A. Compositions aqueuses pour peintures durcissables sous rayonnement
CN102516961B (zh) * 2011-11-15 2013-07-31 中国石油大学(华东) 一种适用于高温油藏的有机/无机交联体系堵剂
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Also Published As

Publication number Publication date
JP2008517125A (ja) 2008-05-22
CN1878812A (zh) 2006-12-13
DE102004050775A1 (de) 2006-04-20
TNSN07143A1 (en) 2008-11-21
KR20070067148A (ko) 2007-06-27
WO2006042769A1 (fr) 2006-04-27
CA2584389A1 (fr) 2006-04-27
US20080262144A1 (en) 2008-10-23
BRPI0518215A (pt) 2008-11-04

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