WO2017174443A1 - Dérivés de triméthylolpropane - Google Patents

Dérivés de triméthylolpropane Download PDF

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Publication number
WO2017174443A1
WO2017174443A1 PCT/EP2017/057596 EP2017057596W WO2017174443A1 WO 2017174443 A1 WO2017174443 A1 WO 2017174443A1 EP 2017057596 W EP2017057596 W EP 2017057596W WO 2017174443 A1 WO2017174443 A1 WO 2017174443A1
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WIPO (PCT)
Prior art keywords
compositions
coating
compounds
trimethylolpropane
acrylic acid
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PCT/EP2017/057596
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German (de)
English (en)
Inventor
Christina HAAF-KLEINHUBBERT
Sirus Zarbakhsh
Juergen Baro
Katrin BECKER
Mathieu BLANCHOT
Sebastian MIRTSCHIN
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Basf Se
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Publication of WO2017174443A1 publication Critical patent/WO2017174443A1/fr

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    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds

Definitions

  • the present invention relates to trimethylolpropane derivatives of special structure which are suitable for coating the surfaces of solid substrates.
  • DE-A-102010044206 describes radiation-curable mixtures obtainable by reacting (meth) acrylic acid with 3.0- to 4.0-fold propoxylated glycerol, followed by removal of excess (meth) acrylic acid from the resulting reaction mixture by means of an aqueous extraction.
  • EP-A-680.985 describes a process for the preparation of radiation-curable acrylates, in which in a first stage hydroxy compounds are reacted with (meth) acrylic acid and the resulting reaction product is subsequently reacted with epoxides in or before the subsequent second stage.
  • the hydroxy compounds may be polyols, in particular trimethylolpropane, glycerol or pentaerythritol.
  • the polyols may be oxalkylated, it being merely disclosed that the degree of alkoxylation may be 0 to 10 and preferably 1 to 10.
  • the cured coatings, especially the UV-cured coatings should have good properties in terms of hardness and elasticity as well as chemical and food resistance especially with regard to black tea and banana.
  • Another object was to achieve a good film course in the coating of surfaces, in particular a reduction of specks.
  • Another task was the achievement of good values in terms of the modulus of elasticity and creep.
  • the invention initially trimethylolpropane derivatives (I), obtainable by reacting in a first step, compositions (II) with (meth) acrylic acid ( ⁇ ), wherein the compositions (II) are compositions which thereby It is possible to add ethylene oxide to trimethylolpropane, wherein the compositions ( ⁇ ) have an OH number (hydroxyl number) in the range of 538 to 572 mg KOH / g - measured according to DIN 53240 -, wherein in the reaction of the compositions ( ⁇ ) with (Meth) acrylic acid ( ⁇ ), the reaction ratios of the reactants adjusted so that per mole of OH groups of the compositions (II) 0.8 to 1.3 mol of (meth) acrylic acid ( ⁇ ) is used, and the reaction mixture obtained in the first step in a second step with one or more polyfunctional epoxides (IV), with the proviso that the acid number of the reaction mixture obtained in the second step amounts to 10 mg KOH per g of substance or less t.
  • the term "reacted" in the second step implies that the oxirane groups of the compounds (IV) used reactivate, meaning that at the end of the second step, there are no longer any free compounds (IV), in other words the epoxide (IV) is used in step 2 in an amount that it completely reacted, with the result that in the final product, no free epoxide is present.
  • compositions (II) have an OH number (hydroxyl number) in the range from 554 to 572 mg KOH / g, measured in accordance with DIN 53240.
  • substances (I) whose pendulum hardness (König) in the range of 90 to 180 sec, with simultaneous modulus of elasticity in the range of 2.00 to 2.50 GPa and creep in the range below 150 nm.
  • the substances (I) have an acid number - determined according to ISO 3682 - of less than 5 mg KOH / g.
  • compositions ( ⁇ ) can be prepared per all methods known to the chemist.
  • the compositions ( ⁇ ) are prepared by reacting ethylene oxide in the presence of a base, preferably sodium hydroxide, potassium hydroxide or sodium methoxide, with trimethylolpropane at elevated temperature.
  • the compositions ( ⁇ ) are essentially mixtures of trimethylolpropane, oligo-trimethylolpropanes, ethoxylated trimethylolpropane and ethoxylated oligotrimethylolpropanes.
  • the proportion of trimethylolpropane and oligotrimethylolpropanes in the compositions ( ⁇ ) is less than 0.35 mol - based on the total composition (II).
  • the bases to be used as catalysts for the ethoxylation can also be:
  • Cesium hydroxide trimethylamine, triethylamine, tripropylamine, tributylamine, ⁇ , ⁇ '-dimethylethanolamine, ⁇ , ⁇ '-dimethylcyclohexylamine, dimethylethylamine, dimethylbutylamine, ⁇ , ⁇ '-dimethylaniline, 4-dimethylaminopyridine, ⁇ , ⁇ '-dimethylbenzylamine, pyridine, imidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, 5-methylimidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, 1-hydroxypropylimidazole, 2,4,5-trimethylimidazole, 2-ethylimidazole, 2-ethyl 4-methylimidazole, N-phenylimidazole, 2-phenylimidazole, 4-phenylimidazole, guanidine, alkylated
  • the compounds (IV) are polyfunctional epoxides. Preference is given to using di- and / or trifunctional epoxides.
  • the compounds (IV) are selected from the group consisting of bisphenol A diglycidyl ether and the polyglycidyl ether of pentaerythritol.
  • the compounds (I) can be prepared per all methods known to the chemist. In particular, reference is made in this context to the knowledge of the skilled person that is disclosed in the above-mentioned document DE-A-102010044206.
  • the compounds (I) are preferably prepared as follows: In a first step, the compositions (II) are reacted with (meth) acrylic acid ( ⁇ ), the reaction being carried out under the abovementioned conditions, and that obtained in the first step Reaction mixture in a second step with one or more polyfunctional epoxides (IV), wherein the reaction is carried out so far that the acid number of the reaction mixture obtained in the second step is 10 mg KOH per g of substance or less.
  • the epoxide (IV) is used in an amount such that it completely reacts, thus no more free epoxide is present in the end product.
  • the acid number of the reaction mixture used in the second step is preferably adjusted to a value in the range from 20 to 210 mg KOH / g of substance. On the one hand, this can be done by appropriately selecting the proportions of the reactants in the first step; if desired, it can also be done by additionally metering (meth) acrylic acid after carrying out the first step and before carrying out the second step.
  • Another subject of the invention are coating compositions comprising one or more trimethylolpropane derivatives (I). Preference is given to coating compositions whose compounds (I) are those which are prepared by using acrylic acid as compound ( ⁇ ). Another subject of the invention is the use of the compounds (I) for coating the surfaces of solid substrates. The nature of the substrate is not limited per se.
  • suitable substrates are for example textile, leather, metal, plastic, glass, wood, paper or cardboard.
  • Preferred substrates are wood and paper.
  • Another subject of the invention is the use of coating compositions comprising one or more trimethylolpropane derivatives (I) for coating the surfaces of solid substrates.
  • the nature of the substrate is not limited per se.
  • suitable substrates are For example, textile, leather, metal, plastic, glass, wood, paper or cardboard.
  • Preferred substrates are wood and paper.
  • coating compositions encompasses any type of compositions which are applied to the surface of a substrate to be coated and then cured, if appropriate after previous drying, in particular the term “coating compositions” includes all types of coatings.
  • lacquer is to be understood as meaning a coating composition which may be liquid or else powdery and which is applied thinly in thin layers to an article, ie the substrate to be coated, and then cured. Compare also the section below on the term “coating”.
  • the coating compositions of the invention may additionally comprise further radiation-curable compounds and further typical coatings additives, for example antioxidants, stabilizers, activators (accelerators), fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents , Viscosity modifiers, plasticizers or chelating agents.
  • the coating compositions according to the invention may also comprise further radiation-curable components which are not encompassed by the formula (I).
  • chelating agents e.g. Ethylenediaminetic acid and its salts and ß-diketones be used.
  • Suitable fillers include silicates, e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonate, etc.
  • silicates e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonate, etc.
  • Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin® grades from Ciba Specialty Chemicals) and benzophenones. These may be used alone or together with suitable radical scavengers, for example sterically prevented amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or their derivatives, e.g. As bis (2,2,6,6-tetra-methyl-4-piperi-dyl) sebacinate used. Stabilizers are usually used in amounts of from 0.1 to 5.0% by weight, based on the solid components contained in the preparation.
  • Pigments may also be included in the coating compositions. Pigments are according to CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995 with reference to DIN 55943 particulate "practically insoluble in the application medium, inorganic or organic, colored or achromatic colorants". In this case, practically insoluble means a solubility at 25 ° C. under 1 g / 1000 g of application medium, preferably below 0.5, more preferably below 0.25, even more preferably below 0.1 and in particular below 0.05 g / 1000 g of application medium.
  • a pigment is used, care must be taken that either the electron beam curing is carried out or that a photoinitiator is used which can be activated despite the pigmentation by the irradiated radiation, for example by the photoinitiator having a significant absorbance in a wavelength range in which the pigment is sufficiently permeable to the incident radiation. It is a preferred embodiment of the present invention not to use pigment and to use the coating composition in clearcoats.
  • pigments include any systems of absorption and / or effect pigments, preferably absorption pigments. Number and selection of the pigment components are not subject to any restrictions. They can be adapted to the particular requirements, for example the desired color impression, as desired.
  • Effect pigments are to be understood as meaning all pigments which have a platelet-like structure and impart special decorative color effects to a surface coating.
  • the effect pigments are, for example, all effect pigments which can usually be used in vehicle and industrial coating.
  • Examples of such effect pigments are pure metal pigments; such as aluminum, iron or copper pigments;
  • Interference pigments such as titanium dioxide-coated mica, iron oxide-coated mica, mixed oxide coating teter mica (eg with titanium dioxide and Fe 2 O 3 or titanium dioxide and Cr 2 O 3 ), metal-oxide-coated aluminum, or liquid-crystal pigments.
  • the coloring absorption pigments are, for example, customary organic or inorganic absorption pigments which can be used in the coatings industry.
  • organic absorption pigments are azo pigments, phthalocyanine, quinacridone and pyrrolopyrrole pigments.
  • Mono- and / or bisacylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure® TPO from BASF SE), ethyl 2,4,6-trimethylbenzoylphenylphosphinate (TPO-L der
  • Benzophenones hydroxyacetophenones, phenylglyoxylic acid and its derivatives or mixtures of these photoinitiators. Examples which may be mentioned are: benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, valerophenone, hexanophenone, ⁇ -phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, 4-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'- Methoxyacetophenone, ⁇ -methylanthraquinone, tert-butylanthraquinone, anthraquinone-carboxylic acid ester, benzaldehyde, ⁇ -tetralone, 9-acetylphenanthrene, 2-acetylphenanthren
  • non- or slightly yellowing photoinitiators of the phenylglyoxalate ester type are also suitable.
  • mixtures of different photoinitiators include, for example, 2-hydroxy-2-methyl-1-phenylpropan-2-one and 1-hydroxycyclohexyl phenyl ketone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 2-hydroxy 2-methyl-1-phenyl-propan-1-one, benzophenone and 1-hydroxycyclohexyl-phenylketone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and 1-hydroxy-cyclohexyl-phenylketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2,4,6-trimethylbenzophenone and 4-methylbenzophenone or 2,4,6-trimethylbenzophenone and 4-methylbenzophenone and 2,4,6-trimethylbenzoy
  • Preferred photoinitiators are:
  • the coating compositions preferably contain the photoinitiators in an amount of 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, in particular 0.2 to 5% by weight, based on the total amount of curable material present in the coating compositions components.
  • Another object of the invention is a process for coating the surfaces of solid substrates, wherein one or more compounds (I) or coating compositions containing one or more compounds (I) applied to the surface of a solid substrate and then performs radiation curing, in particular by means UV light. It is preferred that the radiation curing is a curing with UV light of the wavelength in the range of 200 to 500 nm.
  • Coating also referred to as “coating” means processes which serve to apply a firmly adhering layer to the surface of a workpiece - the substrate.
  • the applied layer is called a coating.
  • the usual coating methods differ in the way in which the coating compositions are applied in chemical, mechanical, thermal and thermomechanical processes.
  • UV curing is preferred, which induces chemical crosslinking of the compounds (I) contained in the coating compositions.
  • the coating of the surfaces of solid substrates with the compounds (I) to be used according to the invention is carried out by customary methods known to the person skilled in the art, wherein the desired compound (I) or a coating composition which contains one or more compounds (I) in the desired strength the substrate is applied and at least partially radiation hardened. In this case, complete radiation curing is preferred. If desired, this process can be repeated once or several times.
  • the application to the substrate can in a known manner, for. Example by spraying, filling, doctoring, brushing, rolling, rolling, casting, laminating, injection molding or co-extrusion, preferably by spraying and rolling.
  • a spraying method e.g. Use air pressure, airless or electrostatic spray application.
  • UV light or electron radiation is preferred.
  • UV light is preferred in the wavelength range of 200 to 500 nm, and more preferably 250 to 400 nm.
  • the coating thickness is preferably adjusted so that the coating thickness of the uncured acrylate is in a range of about 3-1000 g / m 2 and preferably 10-200 g / m 2 .
  • dry film thickness is understood to mean the layer thickness of a dried or hardened coating.
  • drying includes the fact that solvents present in a coating composition, for example water or organic solvents, have evaporated.
  • hardening implies that crosslinking of the coating composition takes place.
  • the radiation curing can be carried out under an oxygen-containing atmosphere or under inert gas, the latter being preferred.
  • Suitable radiation sources for radiation curing are, for example, low-pressure mercury vapor lamps, medium-pressure lamps with high-pressure lamps and fluorescent tubes, LED lamps, pulse emitters, metal halide emitters, lasers, pulsed lamps (flashlight), halogen lamps, electronic flash devices, whereby radiation curing without photoinitiator is possible, or excimer emitters , It is also possible to use a plurality of radiation sources for radiation curing, for example two to four. If desired, these can also radiate in different wavelength ranges.
  • the irradiation may optionally also in the absence of oxygen, for. B. under inert gas atmosphere, carried out.
  • inert gases are preferably nitrogen, noble gases, carbon dioxide, or combustion gases.
  • Particularly suitable amines are: compounds with primary or secondary amines having a molecular weight below 1000 g / mol. These include, for example, primary monoamines such as C 1-2 o-alkylamines, in particular n-butylamine, n-hexylamine, 2-ethylhexylamine, octadecylamine and cycloaliphatic amines cyclopentylamine or cyclohexylamine or ether-group-containing primary amines such as methoxypropylamine.
  • primary monoamines such as C 1-2 o-alkylamines, in particular n-butylamine, n-hexylamine, 2-ethylhexylamine, octadecylamine and cycloaliphatic amines cyclopentylamine or cyclohexylamine or ether-group-containing primary amines such as methoxypropylamine.
  • secondary amines include di-C 1 -C 20 -alkylamines, in particular diethylamine, di-n-butylamine, di-n-hexylamine, and di-isopropylamine.
  • alkanolamines for example mono- or diethanolamine, dimethylethanolamine, aminoethoxyethanol, 2-aminopropan-1-ol and diisopropanolamine, are mentioned.
  • Viscosity The viscosity of the substances as such was measured with a Brookfield viscometer at 25 ° C, speed gradient of 1000 s-1, according to DIN EN ISO 3219 / A.3. Acid value: Measured according to DIN EN ISO 2114
  • Pendulum damping The pendulum damping (often referred to as pendulum hardness) of coatings which resulted when the substances to be tested had been applied to the surfaces of solid substrates and cured by UV radiation, the so-called King pendulum hardness, were measured according to DIN 53157. In this method, the pendulum damping is specified in seconds.
  • Hazenf arbiere The Hazenf arbiere was measured with the Lange Lico 400 device in accordance with DIN EN ISO 6271.
  • Hardening process The liquid acrylates were mixed with 5 wt% Irgacure 500, applied with a doctor blade (120 ⁇ slit width) on Bonder®Blech and glass, then cured with 1900 mJ / m (mercury vapor lamp), at a belt speed of lOm / min under nitrogen.
  • an IST UV system was used (type: M-40-2xl-R-TR-SLC-SO-Inert, lamp 1: IST UV lamp M400 U2HC, lamp 2: IST UV lamp M400 U2H ).
  • the paint properties were determined after storage in a climate chamber for at least 24 hours.
  • Chemical or food resistance The chemical test with black tea and with banana pieces of a ripe banana (slice thickness 0.5 cm) was carried out in accordance with DIN 68861-1, the exposure time was 48 hours. The evaluation was carried out according to DIN EN12720: 1997-10: scale from 5 to 1, where 5 represents the best grade (no change). Examples
  • Comparative Examples VI to V3 were prepared, each having different degrees of EO.
  • TMP trimethylolpropane
  • Step 1 659 g of the composition prepared according to Example 1, 400 g of methylcyclohexane, 2 times 270.44 g of acrylic acid (one portion was added immediately, the other after 3 hours reaction time), 1.2 g Kerobit TBK, 3.6 g methylhydroquinone, 0.036 g Phenothiazine and 1.2 g H3PO2 were charged to the template. Then, 6 g of sulfuric acid (catalyst) was added. The Temperature was raised to 99 - 107 ° C and kept in this temperature range. The progress of the reaction was determined by the amount of the reaction water formed. After about 12 hours the reaction was complete and the solvent was removed at reduced pressure.
  • sulfuric acid catalyst
  • the acid number of the reaction mixture was 39 mg KOH / g substance. 680 g were taken and much acrylic acid added to this until an acid number of 44 mg KOH / g substance was reached. Then, 88.40 g of bisphenol A diglycidyl ether (commercial product Epikote 828) and 20.10 g of tetrabutylammonium bromide were added and the mixture was heated to 108 ° C for 5 hours.
  • Comparative Example C4 were prepared, the substance according to Comparative Example VI esterified in the first step with acrylic acid and the reaction was carried out in the second step bisphenol A diglycidyl ether.
  • the substance according to Comparative Example C4 and the substance according to Example 2 were characterized and the corresponding values can be taken from Table 2:

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Abstract

L'invention concerne des dérivés de triméthylolpropane (I), qu'on obtient par une première étape consistant à faire réagir des compositions (II) avec de l'acide (méth)acrylique (III), les compositions (II) étant des compositions obtenues par addition d'oxyde d'éthylène sur du triméthylolpropane, les compositions (II) présentant un IOH (indice d'hydroxyle) compris dans une plage de 538 à 572 mg KOH/g mesuré selon DIN 53240, en réglant les conditions réactionnelles des réactifs lors de la réaction des compositions (II) avec l'acide (méth)acrylique (III) de manière à utiliser de 0,8 à 1,3 mole d'acide (méth)acrylique (III) par mole de groupes OH des compositions (II), et une seconde étape consistant à faire réagir le mélange réactionnel obtenu à la première étape avec un ou plusieurs époxydes mutlifonctionnels (IV), à condition que l'indice d'acide du mélange réactionnel obtenu à la deuxième étape soit égal ou inférieur à 10 mg de KOH par g de substance. Ces compositions (I) sont appropriées pour le revêtement de surfaces de substrats solides.
PCT/EP2017/057596 2016-04-08 2017-03-30 Dérivés de triméthylolpropane WO2017174443A1 (fr)

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EP16164359 2016-04-08
EP16164359.8 2016-04-08

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EP3649099B1 (fr) * 2017-07-03 2023-06-07 Hilti Aktiengesellschaft Composés de méthacrylate d'époxy et leur utilisation

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DE4410014A1 (de) * 1993-03-23 1994-09-29 Toa Gosei Chem Ind Härtungszusammensetzung und Verfahren zum Imprägnieren von Holz
EP0680985A1 (fr) 1994-05-04 1995-11-08 Basf Aktiengesellschaft Procédé de préparation d'acrylates durcissables par irradiation
EP0738741A2 (fr) * 1995-03-24 1996-10-23 Bayer Ag Epoxy(méth)acrylates, un procédé pour leur préparation et leur utilisation
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WO2004092289A1 (fr) * 2003-04-17 2004-10-28 Cognis Deutschland Gmbh & Co. Kg Masses radiodurcissables
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EP0586849A2 (fr) * 1992-08-05 1994-03-16 Bayer Ag Aminoacrylates, procédé pour leur préparation et leur utilisation
DE4410014A1 (de) * 1993-03-23 1994-09-29 Toa Gosei Chem Ind Härtungszusammensetzung und Verfahren zum Imprägnieren von Holz
EP0680985A1 (fr) 1994-05-04 1995-11-08 Basf Aktiengesellschaft Procédé de préparation d'acrylates durcissables par irradiation
EP0738741A2 (fr) * 1995-03-24 1996-10-23 Bayer Ag Epoxy(méth)acrylates, un procédé pour leur préparation et leur utilisation
DE10206831A1 (de) * 2002-02-18 2003-08-28 Basf Ag Beschichtungen für Trägermaterialien zur Erreichung einer Sauerstoffbarriere
WO2004092289A1 (fr) * 2003-04-17 2004-10-28 Cognis Deutschland Gmbh & Co. Kg Masses radiodurcissables
US20060030634A1 (en) * 2004-08-04 2006-02-09 Dean Roy E Radiation curable, sprayable coating compositions
DE102010044206A1 (de) 2009-11-25 2011-05-26 Basf Se Verfahren zur Herstellung von strahlungshärtbaren (Meth)Acrylaten

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3649099B1 (fr) * 2017-07-03 2023-06-07 Hilti Aktiengesellschaft Composés de méthacrylate d'époxy et leur utilisation

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