EP1838755A1 - Polyesters amorphes insatures, aqueux, modifies de façon a etre durcissables par rayonnement - Google Patents

Polyesters amorphes insatures, aqueux, modifies de façon a etre durcissables par rayonnement

Info

Publication number
EP1838755A1
EP1838755A1 EP05823963A EP05823963A EP1838755A1 EP 1838755 A1 EP1838755 A1 EP 1838755A1 EP 05823963 A EP05823963 A EP 05823963A EP 05823963 A EP05823963 A EP 05823963A EP 1838755 A1 EP1838755 A1 EP 1838755A1
Authority
EP
European Patent Office
Prior art keywords
unsaturated
radiation
aqueous
curable
acid
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Withdrawn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
EP05823963A
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
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 Degussa GmbH filed Critical Degussa GmbH
Publication of EP1838755A1 publication Critical patent/EP1838755A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/205—Compounds containing groups, e.g. carbamates

Definitions

  • the invention relates to aqueous, radiation-curable, unsaturated, amorphous polyesters, a process for their preparation and their use.
  • VOC volatile organic compounds
  • the film-forming components in the coating material are relatively low molecular weight and therefore low viscosity, so that high proportions of organic solvents can be dispensed with.
  • Durable coatings are obtained by applying a high molecular polymer network through e.g. B. UV light or electron beam initiated crosslinking reactions.
  • reactive diluents which are mostly mono-, di- or higher-functional acrylate monomers, are added so that the viscosity of the quasi-no-VOC systems is sufficiently low.
  • the reactive thinners are not harmless from a toxicological point of view.
  • the low molecular weight reactive thinners can penetrate the substrate and are no longer available for a crosslinking reaction, which can lead to delamination and / or exudation.
  • As a result of the network formation there is a volume shrinkage due to the high proportion of low molecular weight compounds, which is reported in the literature as a reason for the sometimes poor adhesion of radiation-curable coating materials on different substrates [Surface Coatings International Part A, 2003/06, pp. 221-228].
  • Viscosity is independent of the molecular weight of the polymers (K. Buysens, M. Tielemans, T.
  • Unsaturated polyester resins are known. They are produced by the condensation of saturated and unsaturated dicarboxylic acids or their anhydrides with diols. Their properties largely depend on the type and quantitative ratio of the starting materials.
  • ⁇ , ⁇ -unsaturated acids are mostly used as carriers of the polymerizable double bonds, primarily maleic acid or its anhydride or fumaric acid; Unsaturated diols are of minor importance.
  • the reactive double bonds in the polyester molecule are therefore “diluted” by condensing in saturated aliphatic or aromatic dicarboxylic acids.
  • Straight-chain and / or branched diols are used as alcohol components.
  • the individual UP resin types differ not only in the components used for their preparation, but also in that Quantity ratio of saturated to unsaturated acids, which determines the crosslinking density during the polymerization, the degree of condensation, ie the molecular weight, the acid and OH number, ie the type of end groups in the chain molecules, the monomer content and the type of additives (Ullmann's Encyclopedia of Industrial Chemistry, VOL A21, pp. 217 ff, 1992).
  • UP resins based on dicidol as a diol component are e.g. B. known from DE 953 117, DE 22 45 110, DE 27 21 989, EP 0 114 208, EP 0 934 988.
  • DE 953 117 describes a process for the production of unsaturated polyesters, characterized in that unsaturated dicarboxylic acids are reacted with polycyclic, polyhydric alcohols, the hydroxyl groups of which are distributed over different rings of an appropriately condensed ring system.
  • These polyesters can be polymerized with vinyl compounds such as styrene, alkylstyrene, chlorostyrene, vinylnaphthalene and vinyl acetate, whereupon non-sticky films are obtained.
  • DE 953 117 In contrast to the dicidol mixture of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane used in the present invention and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, DE 953 117 only uses an undefined diol with a suspected structure, similar to dicidol. In addition, vinyl compounds which contain only one double bond but no acrylic double bond are optionally used there. A modification of the polyesters with acrylic double bonds is not described.
  • Aromatic vinyl compounds as described in DE 953 117 can also disadvantageously e.g. resistance properties such as Weathering stabilities, which is why they are hardly used in high-quality adhesives and / or coating materials. As detailed in-house experiments have shown, only an improvement in the freedom from tack is achieved with resin-vinyl monomer compositions as described in DE 953 117.
  • the compounds produced in the present invention are distinguished in that the adhesion of coating materials is improved, while at the same time improved corrosion protection, higher hardness, improved gloss and polymer content with the same viscosity of the paint or adhesive, and low volume shrinkage during crosslinking and good color stability of the cross-linked polymer.
  • DE 22 45 110 describes polyester compositions composed of unsaturated polyesters, vinyl monomers, activators and additives for the production of coatings which can be cured by means of IR radiation and which are said to improve the grindability, curing properties and stackability.
  • the present invention is concerned with UV or electron beam curing adhesive and coating material systems.
  • WO 89/07622 describes radiation-resistant polyesters and polycarbonates containing acrylic styrene, which could possibly contain dicidol, for the packaging of e.g. Foodstuffs such as fruit juices, soft drinks, wine, etc.
  • the unsaturated polyesters on which the present invention is based are free from acylstyryl units and are also radiation-curing.
  • compositions which are likewise not suitable for radiation-induced crosslinking are described in DE 102 05 065.
  • the polyester resins used there only contain dicyclopentadiene which are not accessible for direct esterification.
  • particularly pressure-resistant and therefore high-priced reactors have to be used for the production, which is not recommended from an economic point of view.
  • DE 102 61 006 and DE 102 61 005 describe aqueous, unsaturated polyesters which, however, can only crosslink in a radiation-induced manner via the unsaturated dicarboxylic acids.
  • the reactivity of unsaturated polyesters towards radiation-induced crosslinking reactions is low, which limits their use in applications which are dependent on high throughputs for economic reasons.
  • the object of the present invention was to find an aqueous, adhesion-improving composition which has the properties of e.g. aqueous, radiation-curable adhesives and coating materials, e.g. the adhesion, improved and at the same time has a high corrosion protection, high hardness, improved gloss of the coating and a low viscosity. At the same time, the reactivity to the radiation-induced crosslinking reaction should be high.
  • the invention therefore relates to aqueous, radiation-curable, unsaturated, amorphous polyesters consisting essentially of
  • Another object of the invention is the use of aqueous, radiation-curable modified, unsaturated, amorphous polyester consisting essentially of
  • Main component, base component or additional component in aqueous coating materials, adhesives, printing inks and inks, polishes, glazes, pigment pastes, leveling compounds, cosmetic articles and / or sealants and insulation materials, in particular to improve adhesion properties, gloss, resistance to solvents and chemicals as well as hardness at the same time as high Reactivity.
  • the aqueous, radiation-curable, unsaturated, amorphous polyesters are characterized by a) a content of non-volatile constituents of 20 to 60% b) a solvent content of 0 to 20% c) a viscosity at 20 ° C of 20 to 750 mPa-s
  • compositions according to the invention can be mixed with aqueous, acrylated polyesters, polyacrylates, polyester urethanes, epoxy acrylates and / or polyether acrylates as well as alkyd resins, ketone-formaldehyde resins, ketone resins and / or unsaturated polyesters.
  • compositions of the invention can e.g. can be used as binders in aqueous, radiation-curing coating materials and form corrosion-resistant coatings by radical polymerization.
  • the good adhesion and the possibility of undergoing crosslinking reactions predestine the resins according to the invention for corrosion protection.
  • adhesion to different plastics is improved.
  • the interlayer adhesion to overlying and underlying boundary layers is also improved.
  • Coating materials which contain an additive according to the invention are also notable for high gloss and good flow. Due to the high reactivity of the products according to the invention, use in areas in which high throughput speeds are required during curing is advantageous.
  • the aqueous, radiation-curable, unsaturated, amorphous polyesters are used in particular in aqueous, radiation-curing coating materials, adhesives, laminations, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetic articles, packaging materials and / or sealants and insulation materials, in particular to improve the adhesive properties and the hardness used.
  • This gives very good adhesion properties to different substrates such as.
  • polyethylene, polypropylene or polycarbonate, polymethyl methacrylate, ABS but also for glass, paper, cardboard, cardboard, wood, leather and textiles as well as ceramics.
  • aqueous, radiation-curable, adhesion-improving products of modified, unsaturated, amorphous polyesters according to the invention are described in more detail below.
  • the unsaturated, amorphous polyester resins of component A) are reacted obtained an alcohol component and an acid component.
  • a dicidol mixture of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane and 5 , 8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, where each isomer can be present in the mixture in a proportion of 20 to 40% and the sum of the three isomers 90 to 100%, preferably 95 to 100%, and the mixture is at least 5% present in the alcohol component of the polyester.
  • the isomer content of the dicidol mixture can be qualitatively and quantitatively e.g. B.
  • the dicidol mixture can contain up to 10% of further isomers of dicidol and / or trimeric and / or higher isomeric diols of the Diels-Alder reaction product from cyclopentadiene.
  • the alcohol component advantageously consists of 20%, preferably 50%, particularly preferably 90%, very particularly preferably 100% dicidol mixture, this particularly preferably containing 95 to 100% of the above three isomeric compounds.
  • the alcohol component can contain further linear and / or branched, aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols.
  • Preferred additional alcohols are ethylene glycol, 1,2- and / or 1,3-propanediol, diethylene, dipropylene, triethylene, tetraethylene glycol, 1,2- and / or 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, cyclohexane dimethanol, glycerol, hexanediol, neopentylglycol, trimethylolethane, trimethylolpropane and / or pentaerythritol and bisphenol A, B, C, F, norbornylene glycol, 1,4-benzyldimethanol and ethanol
  • the unsaturated, amorphous polyester resins contain as the starting acid component at least one ⁇ , ⁇ -unsaturated dicarboxylic acid.
  • the unsaturated polyester resins preferably contain citraconic, fumaric, itaconic, maleic and / or mesaconic acid.
  • phthalic acid isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid, methyltetra-, methylhexahydrophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, isononellitic acid, 2-ethanoic acid acid, 2-ethanoic acid; are hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedioic acid, adipic acid, azelaic acid, trimellitic acid (anhydride) and / or phthalic acid (anhydride).
  • the alcohol component is contained in a molar ratio of 0.5 to 2.0 to 1 to the acid component, preferably 0.8 to 1.5 to 1.
  • the alcohol component is particularly preferably reacted in a molar ratio of 1.0 to 1.1 to 1 instead of the acid component.
  • the unsaturated, amorphous polyesters can have an acid number between 1 and 200 mg KOH / g, preferably between 1 and 150, particularly preferably between 1 and 100 mg KOH / g and an OH number between 1 and 200 mg KOH / g, preferably between 1 and 150, particularly preferably between 1 and 100 mg KOH / g.
  • the glass transition temperature, Tg, of the radiation-curable, unsaturated, amorphous polyester varies from -30 to +100 ° C, preferably from -20 to +80 ° C, particularly preferably from - 10 to + 60 ° C.
  • the unsaturated polyesters consist of an alcohol component with at least 90%, preferably 95%, particularly preferably 100% of the dicidol mixture of the isomeric compounds 3,8- Bis (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane and from fumaric acid and / or maleic acid (anhydride) in a diol / acid ratio of 0.9 to 1.1 to 1.
  • the polyesters contain the above starting components as under I, but additionally further acids selected from adipic acid, trimellitic acid (anhydride), dodecanedioic acid, 1,2-cyclohexanedicarboxylic acid and / or phthalic acid (anhydride), it being possible for the ratio of the ⁇ , ⁇ -unsaturated to the additional acid to vary from 2 to 1 to 1 to 4. Ratios of approximately 1 to 1 to 1 to 2 are preferred.
  • polyesters generally have acid numbers of 1 to 200 mg KOH / g, preferably 1 to 150 mg KOH / g, particularly preferably 1 to 100 mg KOH / g, OH numbers from 1 to 200 mg KOH / g, preferably 1 - 150 mg KOH / g, particularly preferably 1 - 100 mg KOH / g and a Tg of -30 to +100 ° C, preferably -20 to +80 ° C, particularly preferred -10 to +60 ° C.
  • Suitable as component B) are (meth) acrylic acid derivatives such as. B.
  • (meth) acryloyl chloride glycidyl (meth) acrylate, (meth) acrylic acid and / or their low molecular weight alkyl esters and / or anhydrides alone or in a mixture.
  • amino- or hydroxyalkyl (meth) acrylates whose alkyl spacers have one to 12, preferably 2 to 8, particularly preferably 2 to 6 carbon atoms.
  • isocyanates which have an ethylenically unsaturated group, such as.
  • B. (meth) acryloyl isocyanate, ⁇ , ⁇ -dimethyl-3-isopropenylbenzyl isocyanate, (meth) acrylic alkyl isocyanate with alkyl spacers having one to 12, preferably 2 to 8, particularly preferably 2 to 6 carbon atoms, such as.
  • B. methacrylic ethyl isocyanate, methacrylic butyl isocyanate.
  • component B) there are reaction products of amino- or hydroxyalkyl (meth) acrylates, the alkyl spacers of which have from one to 12, preferably from 2 to 8, particularly preferably from 2 to 6, carbon atoms, and diisocyanates such as B.
  • cyclohexane diisocyanate methylcyclohexane, Ethylcyclohexandiisocyanat, propyl cyclohexane diisocyanate, diisocyanate Methyldiethylcyclohexandiisocyanat, phenylene, tolylene, bis (isocyanatophenyl) methane, Propandiisocyanat, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, such as hexamethylene diisocyanate (HDI) or l, 5-diisocyanato-2- methylpentane (MPDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, such as 1,6-diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhex
  • Examples are the reaction products in a 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 produced by di-, trimerization, allophanatization, biuretization and / or urethanization of the simple diisocyanates with more than two isocyanate groups per molecule, for example the reaction products of these simple diisocyanates, such as IPDI, HDI and / or H 12 MDI with polyhydric alcohols (e.g. glycerin, trimethylolpropane,
  • Pentaerythritol or polyvalent polyamines or the triisocyanurates, which are obtainable by trimerization of simple diisocyanates, such as IPDI, HDI and H 12 MDI.
  • component A) with ⁇ , ⁇ -dimethyl-3-isopropenylbenzyl isocyanate in a molar ratio of 1: 1.5, products of higher hardness are obtained than by using (meth) acrylic ethyl isocyanate and / or hydroxyethyl acrylate-hexamethylene diisocyanate adducts; however, the flexibility is then less.
  • the transfer of the polymers into the aqueous phase can take place directly and without the aid of further additives, possibly after their neutralization with suitable neutralizing agents, in particular if free acid groups are present.
  • the free Acid groups are obtained, for example, by partial reaction of, for example, di-, tri- or polycarboxylic acids such as pyromellitic acid and / or trimellitic acid as component C).
  • a hydrophilic modification can also take place, e.g. by reacting the hydroxy-functional reaction product from A) and B) with a component C) such as e.g. a (poly) isocyanate and / or mixtures of different (poly) isocyanates with compounds which, in addition to the hydrophilic or potentially hydrophilic group - i.e. those groups that only become hydrophilic after neutralization - at least one function that is reactive towards isocyanate groups, e.g. Have hydroxyl or amino groups and are described in EP 0839847.
  • examples of such compounds for the hydrophilic modification of (poly) isocyanates are amino acids, hydroxysulfonic acids, aminosulfonic acids and hydroxycarboxylic acids. Dimethylolpropionic acid and / or 2 - [(2-aminoethyl) amino] ethanesulfonic acid or their derivatives are preferably used (component C)).
  • the hydrophilic modification can also be carried out with nonionic groups or compounds which have already been neutralized.
  • Suitable polyisocyanates for the production of C) are preferably di- to tetrafunctional polyisocyanates. Examples include cyclohexane diisocyanate, methylcyclohexane diisocyanate,
  • TMDI Diisocyanato-2,2,4-trimethylhexane
  • nonane triisocyanate such as 4-iso-cyanatomethyl-l, 8-octane diisocyanate (TIN), decane di- and triisocyanate, undecane di- and triisocyanate, dodecane di- and triisocyanates, isophorone diisocyanate ( IPDI), dicyclohexylmethane-4,4'-diisocyanate
  • Another preferred class of polyisocyanates are the compounds produced by di-, trimerization, allophanatization, biuretization and / or urethanization of the simple diisocyanates with more than two isocyanate groups per molecule, for example the reaction products of these simple diisocyanates, such as IPDI, TMDI, HDI and / or H 12 MDI with polyhydric alcohols (eg glycerol, trimethylolpropane, pentaerythritol) or polyhydric polyamines or the triisocyanurates which can be obtained by trimerizing the simple diisocyanates such as IPDI, HDI and H 12 MDI.
  • polyhydric alcohols eg glycerol, trimethylolpropane, pentaerythritol
  • polyhydric polyamines eglycerol
  • a hydrophilically modified polyisocyanate (C) of dimethylolpropionic acid and / or 2 - [(2-aminoethyl) amino] ethanesulfonic acid or its derivatives and IPDI and / or H 12 MDI and / or HDI in a molar ratio of 1: 2 is particularly preferred.
  • nonionic hydrophilization e.g. take place via suitable polyether polyols, e.g. can be implemented with the above-mentioned polyisocyanates and components A) and B).
  • compositions according to the invention can also contain auxiliaries and additives such as, for example, inhibitors, organic solvents, surface-active substances, oxygen and / or free radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers, thixotropic agents, skin-preventing agents, defoamers, antistatic agents, thickeners, thermoplastic additives, dyes, Pigments, fire protection equipment, internal release agents, fillers and / or blowing agents.
  • auxiliaries and additives such as, for example, inhibitors, organic solvents, surface-active substances, oxygen and / or free radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers, thixotropic agents, skin-preventing agents, defoamers, antistatic agents, thickeners, thermoplastic additives, dyes, Pigments, fire protection equipment, internal release agents, fillers and / or blowing agents.
  • polyesters of component A) according to the invention are produced by (semi) continuous or discontinuous esterification and condensation of the starting acids and alcohols in a single-stage or multi-stage procedure. Then polyester A) is reacted with components C) and B), or in the reverse order, with components B) and C). The reaction can take place in the melt or in solution of a suitable solvent.
  • the invention also relates to a process for the preparation of aqueous, radiation-curable, unsaturated, amorphous polyesters consisting essentially of A) at least one unsaturated, amorphous polyester, consisting of at least one ⁇ , ⁇ -unsaturated dicarboxylic acid component and an alcohol component, the alcohol component being composed of a dicidol mixture of the isomeric compounds 3,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane, 4,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane and 5,8-bis (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane, each isomer into one
  • component C) at least one compound with at least one hydrophilic and / or potentially hydrophilic group by reacting the starting components to produce component A) at a temperature of 150 to 270 ° C., preferably in an inert gas atmosphere, the inert gas having an oxygen content of less than 50 ppm and subsequent reaction with components C) and B), or in reverse order, with components B) and C) in the melt or in solution of a suitable organic solvent, which - if desired - are separated by distillation after production can, at temperatures between 20 and 230 ° C, preferably between 40 and 200 ° C, particularly preferably between 50 and 180 ° C and then dispersing the optionally neutralized resin in water.
  • Suitable auxiliary solvents which do not form a miscibility gap with water at least over wide areas, have a boiling point at atmospheric pressure below 100 ° C and therefore, if desired, easily distillate to a residual content of less than 2% by weight and in particular of less than 0.5% by weight, based on the finished dispersion or aqueous solution, and can be reused.
  • Suitable solvents of this type are, for example, acetone, methyl ethyl ketone or tetrahydroiuran.
  • Higher-boiling solvents such as, for example, n-butyl glycol, di-n-butyl glycol and N-methylpyrrolidone, which then remain in the dispersion, are also fundamentally suitable. Possibly. reactive diluents can be used, ie compounds which have a relatively low viscosity and at the same time can undergo crosslinking reactions initiated by radiation. These compounds also remain in the later aqueous dispersion.
  • a suitable neutralizing agent can be added to the products according to the invention, which then gives water-dilutable, water-dispersible or water-soluble products.
  • the resins produced according to the invention can be neutralized with inorganic and / or organic bases, such as e.g. Ammonia or organic amines.
  • Primary, secondary and / or tertiary amines such as e.g. 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 are particularly preferred in the case of anionic potential groups.
  • So-called cationic potential ionogenic groups can be neutralized with inorganic and / or organic acids, e.g. 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 30 to 130% (0.3 to 1.3) of the amount of neutralization, preferably 40 to 100% (0.4 to 1), particularly preferably 60 to 100 % (0.6 to 1) required for stoichiometric neutralization.
  • reaction product of A), B) and C) can, if appropriate, be combined with further hydrophilic and / or non-hydrophilic resins and / or further components and then dispersed together.
  • I will to a solution or melt of component A) which contains a partially converted di-, tri- or polycarboxylic acid as component C), the compound which has at least one ethylenically unsaturated group and at the same time at least one group which is reactive towards A) (component B) ), optionally in the presence of a suitable catalyst.
  • the temperature of the reaction is selected depending on the reactivity of the components to one another. Temperatures between 20 and 230 ° C., preferably between 40 and 200 ° C., particularly preferably between 50 and 180 ° C., have proven successful in these reaction steps.
  • the neutralized reaction product can be dispersed in water. Alternatively, dispersion can be carried out directly in a water / neutralizing agent mixture.
  • the solvent which may be present can be separated off after the reaction has ended, in which case a solution to dispersion of the product according to the invention is generally obtained.
  • the compound which has at least one ethylenically unsaturated group and at the same time at least one group which is reactive towards A) (component B)), optionally in the presence of a suitable catalyst, is added to a solution or melt of component A).
  • component C) can, for example, be an adduct of 2 mol of diisocyanate and 1 mol Dihydroxycarboxylic acid such as, for example, dimethylolpropionic acid and / or 2 - [(2-aminoethyl) amino] ethanesulfonic acid or their derivatives, if appropriate using a suitable solvent and a suitable catalyst.
  • Dihydroxycarboxylic acid such as, for example, dimethylolpropionic acid and / or 2 - [(2-aminoethyl) amino] ethanesulfonic acid or their derivatives, if appropriate using a suitable solvent and a suitable catalyst.
  • the separately manufactured products are combined and reacted.
  • the temperature of the reaction is selected depending on the reactivity of the components to one another. In these reaction steps, temperatures between 20 and 230 ° C., preferably between 40 and 200 ° C., particularly preferably between 50 and 180 ° C. have proven successful.
  • the reaction can be stopped by adding an amine or alcohol.
  • an amine or alcohol e.g. 1,3-butanediol
  • other properties such as compatibility with other raw materials, e.g. Pigments, vary.
  • the neutralized reaction product can first be neutralized with a suitable neutralizing agent and then the neutralized reaction product can be dispersed in water. Alternatively, dispersion can be carried out directly in a water / neutralizing agent mixture.
  • the solvent which may be present can be separated off after the reaction has ended, in which case a solution to dispersion of the product according to the invention is generally obtained.
  • the resin 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, leveling compounds, cosmetic articles and / or sealants and insulation materials, since they are characterized by fast curing speeds, high blocking resistance and hardness , high gloss, relatively low viscosities and very good adhesion properties and associated with it, have very good corrosion protection effects.
  • Objects can be finished with the aqueous, radiation-curable, unsaturated, amorphous polyesters.
  • these resins can be converted by irradiation into polymeric, insoluble networks which, depending on the content of ethylenically unsaturated groups, give elastomers to thermosets.
  • Dodecanedioic acid and fumaric acid are reacted with dicidol in a ratio of 1: 1.15 at 180 ° C in a nitrogen atmosphere until an acid number of 12 mg KOH / g is reached.
  • the fumaric acid is first esterified with dicidol for one hour and then the dodecanedioic acid is added.
  • the resin is dissolved 50% in acetone.
  • the OH number is 62 mg KOH / g.
  • the OH groups of the polyester are mixed with a 1: 1 mixture consisting of a 1: 1 adduct of hydroxyethyl acrylate and isophorone diisocyanate and a 1: 2 adduct of dimethylolpropionic acid and isophorone diisocyanate at 55 ° C in the presence of 0.1% dibutyltin dilaurate implemented until an NCO number below 0.1% is reached. Then the polymer content is adjusted exactly to 50% with acetone.
  • the dispersion is provided with a polyurethane dispersion in a ratio of 1: 1, applied to a glass plate or bonder sheet and the solvent is evaporated at elevated temperature (30 min, 80 ° C).
  • the films are then cured for about 12 seconds using UV light (medium-pressure mercury lamp, 70 W / optical filter 350 nm).
  • the films are resistant to premium petrol and methyl ethyl ketone.
  • Adhesion to galvanized sheet steel (DIN 53151): 0 Buchholz indentation hardness (DIN 53153): 79 Erichsen depth (DIN 53156):> 9.5 mm pendulum hardness according to König (DIN EN ISO 1522): 118 s
  • adipic acid 1.1 mol of adipic acid are reacted with 3.4 mol of dicidol at 210 ° C. in a nitrogen atmosphere until an acid number below 5 mg KOH / g is reached. Then 1.1 mol of fumaric acid and 0.02% hydroquinone are added. After stirring for 2 h, a vacuum of 20 mbar is applied until an acid number below 5 mg KOH / g is reached. 1300 g of the polyester produced are mixed with 150 g of trimellitic anhydride and stirred at 200 ° C. for 1.5 h until an acid number of about 26 mg KOH / g is reached. The OH number is 56 mg KOH / g.
  • the polyester is mixed with acetone on a
  • the dispersions according to Example II. And III. are mixed with a polyurethane dispersion in proportions of 90/10, 80/20 and 70/30 (polyurethane dispersion / sample dispersion) and provided with 3% Darocur 1173, applied to aluminum sheets and the solvent evaporated at elevated temperature (30 min, 80 ° C) .
  • the films are then cured for about 12 seconds using UV light (medium-pressure mercury lamp, 70 W / optical filter 350 nm).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des polyesters amorphes insaturés, aqueux, modifiés de façon à être durcissables par rayonnement, un procédé de fabrication de ces polyesters et leur utilisation dans des systèmes aqueux durcissables par rayonnement.
EP05823963A 2005-01-19 2005-11-28 Polyesters amorphes insatures, aqueux, modifies de façon a etre durcissables par rayonnement Withdrawn EP1838755A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005002388A DE102005002388A1 (de) 2005-01-19 2005-01-19 Wässrige, strahlungshärtbar modifizierte, ungesättigte, amorphe Polyester
PCT/EP2005/056266 WO2006076974A1 (fr) 2005-01-19 2005-11-28 Polyesters amorphes insatures, aqueux, modifies de façon a etre durcissables par rayonnement

Publications (1)

Publication Number Publication Date
EP1838755A1 true EP1838755A1 (fr) 2007-10-03

Family

ID=36072211

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05823963A Withdrawn EP1838755A1 (fr) 2005-01-19 2005-11-28 Polyesters amorphes insatures, aqueux, modifies de façon a etre durcissables par rayonnement

Country Status (6)

Country Link
US (1) US20080039593A1 (fr)
EP (1) EP1838755A1 (fr)
JP (1) JP2008527153A (fr)
CN (1) CN1898296A (fr)
DE (1) DE102005002388A1 (fr)
WO (1) WO2006076974A1 (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005031271A1 (de) 2005-07-05 2007-01-18 Degussa Ag Verfahren zur Herstellung von strahlenhärtbaren Formulierungen mit erhöhtem Korrosionsschutz auf Metalluntergründen und solche Formulierungen
DE102006000645A1 (de) * 2006-01-03 2007-07-12 Degussa Gmbh Universalpigmentpräparationen
DE102006000646A1 (de) * 2006-01-03 2007-07-12 Degussa Gmbh Zusammensetzung zur Herstellung von Universalpigmentpräparationen
DE102006009079A1 (de) * 2006-02-28 2007-08-30 Degussa Gmbh Formaldehydfreie, carbonylhydrierte Keton-Aldehydharze auf Basis Formaldehyd und ein Verfahren zu ihrer Herstellung
DE102006045041A1 (de) * 2006-09-25 2008-03-27 Evonik Degussa Gmbh Strahlenhärtbare Formulierung, die zu flexiblen Beschichtungen mit erhöhtem Korrosionsschutz auf Metalluntergründen führt
EP2105126A1 (fr) * 2008-03-26 2009-09-30 Bayer MaterialScience AG Compositions cosmétiques décoratives
US8614286B2 (en) * 2008-09-02 2013-12-24 Ppg Industries Ohio, Inc. Biomass derived radiation curable liquid coatings
US8198397B2 (en) * 2008-10-31 2012-06-12 Grupo Petrotemex, S.A. De C.V. Integrated steam heating in polyester production process
US8017723B2 (en) * 2008-10-31 2011-09-13 Grupo Petrotemex, S.A. De C.V. Steam heated polyester production process
US8470926B2 (en) * 2009-03-05 2013-06-25 Dsm Ip Assets B.V. Unsaturated polyester resin
JP5590406B2 (ja) * 2011-02-03 2014-09-17 Ｄｉｃ株式会社 水性ウレタン樹脂組成物、コーティング剤、鋼板表面処理剤ならびに硬化物及び積層物
EP2639272A1 (fr) * 2012-03-13 2013-09-18 Cytec Surface Specialties, S.A. Émulsions aqueuses durcissables par rayonnement d'énergie active
CN105585902A (zh) * 2016-02-23 2016-05-18 佛山市彩贵新型材料有限公司 一种水性uv固化喷涂油墨及其制备方法
CN105504976A (zh) * 2016-02-23 2016-04-20 佛山市彩贵新型材料有限公司 一种陶瓷喷涂水性油墨及其制备方法
CN105585899A (zh) * 2016-02-23 2016-05-18 谭海林 一种水性uv固化陶瓷喷涂油墨及其制备方法
CN105504972A (zh) * 2016-02-23 2016-04-20 谭海林 一种水性uv固化陶瓷油墨及其制备方法
EP3243863A1 (fr) 2016-05-09 2017-11-15 Evonik Degussa GmbH Utilisation de copolymeres sequences dans des colles
KR102444853B1 (ko) 2021-06-04 2022-09-19 에스케이케미칼 주식회사 트리사이클로데칸 디메탄올 조성물 및 이의 제조방법
KR102389695B1 (ko) * 2021-06-18 2022-04-21 에스케이케미칼 주식회사 트리사이클로데칸 디메탄올 조성물 및 이의 제조방법

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE953117C (de) * 1953-12-17 1956-11-29 Huels Chemische Werke Ag Verfahren zur Herstellung von ungesaettigten Polyestern
US4322504A (en) * 1975-09-18 1982-03-30 Hoechst Aktiengesellschaft Resin binders and process for preparing them
US4826903A (en) * 1988-02-22 1989-05-02 Eastman Kodak Company Condensation polymer containing the residue of an acyloxystyrl compound and shaped articles produced therefrom
DE19805008A1 (de) * 1998-02-07 1999-08-12 Huels Chemische Werke Ag Beschichtungen auf Basis thermoplastischer Polyester unter Zusatz eines ungesättigten Polyesters als Zusatzharz
DE19944373A1 (de) * 1999-09-16 2001-03-22 Degussa Katalysator und Verfahren zur Herstellung von farbreduzierten isocyanuratgruppenhaltigen Polyisocyananten
DE10047762A1 (de) * 2000-09-27 2002-04-11 Degussa Pulverförmige, wasserdispergierbare blockierte Polyisocyanataddukte, ein Verfahren zur Herstellung und ihre Verwendung
DE10163783A1 (de) * 2001-12-22 2003-07-03 Degussa Verfahren zur Herstellung epoxidierter Polyalkenylene und Verwendung von Phosphonsäuren und deren Derivaten als Katalysator
DE10212706A1 (de) * 2002-03-21 2003-10-02 Degussa Ungesättigte, amorphe Polyester auf Basis bestimmter Dicidolisomerer
DE10242265A1 (de) * 2002-09-12 2004-03-25 Degussa Ag Haftungsverbessernder Zusatz aus einem ungesättigten, amorphen Polyester
DE10258574A1 (de) * 2002-12-14 2004-07-01 Degussa Ag Polymermodifizierte Harze
DE10258573A1 (de) * 2002-12-14 2004-07-01 Degussa Ag Polymermodifizierte Harze
DE10261006A1 (de) * 2002-12-24 2004-07-08 Degussa Ag Dispersionen amorpher, ungesättigter Polyesterharze auf Basis bestimmter Dicidolisomerer
DE10261005A1 (de) * 2002-12-24 2004-07-08 Degussa Ag Dispersionen amorpher, urethanisierter ungesättigter Polyesterharze auf Basis bestimmter Dicidolisomerer
DE10322845A1 (de) * 2003-05-19 2004-12-16 Degussa Ag Verzweigte,amorphe Makropolyole auf Polyesterbasis mit enger Molekulargewichtsverteilung
DE10326893A1 (de) * 2003-06-14 2004-12-30 Degussa Ag Harze auf Basis von Ketonen und Aldehyde mit verbesserten Löslichkeitseigenschaften und geringen Farbzahlen
DE10338561A1 (de) * 2003-08-22 2005-04-14 Degussa Ag Keton-Aldehydharze, insbesondere Cyclohexanon-Formaldehydharze mit geringem Wassergehalt und hoher thermischer Bestätigkeit und Vergilbungsbeständigkeit sowie ein Verfahren zur Herstellung und Verwendung
DE10338562A1 (de) * 2003-08-22 2005-03-17 Degussa Ag Strahlenhärtbare Harze auf Basis von Keton- und/oder Harnstoff-Aldehydharzen und ein Verfahren zu ihrer Herstellung
DE10338559A1 (de) * 2003-08-22 2005-04-14 Degussa Ag Verfahren zur Herstellung von Keton-Formaldehydharzen
DE10338560A1 (de) * 2003-08-22 2005-03-17 Degussa Ag Strahlenhärtbare Harze auf Basis hydrierter Keton- und Phenol-Aldehydharze und ein Verfahren zu ihrer Herstellung
DE102004005208A1 (de) * 2004-02-03 2005-08-11 Degussa Ag Verwendung strahlenhärtbarer Harze auf Basis hydrierter Keton- und Phenol-Aldehydharze

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006076974A1 *

Also Published As

Publication number Publication date
DE102005002388A1 (de) 2006-07-27
US20080039593A1 (en) 2008-02-14
CN1898296A (zh) 2007-01-17
WO2006076974A1 (fr) 2006-07-27
JP2008527153A (ja) 2008-07-24

Similar Documents

Publication Publication Date Title
WO2006076974A1 (fr) Polyesters amorphes insatures, aqueux, modifies de façon a etre durcissables par rayonnement
EP1761582B1 (fr) Composition d'amelioration d'adherence, durcissable par rayonnement, formee de polyesters insatures amorphes et de diluants reactifs
EP1799742A1 (fr) Polyesters amorphes, insatures, modifies, durcissables par rayonnement
WO2006045661A1 (fr) Utilisation d'une dispersion aqueuse a base d'un polyester amorphe insature, a base de dicidolisomeres determines
DE69821786T2 (de) Pulverbeschichtungszusammensetzung
EP1433803B1 (fr) Dispersions des polyester résines amorphes, urethannisées et non saturées à base des certaines dicidol isomères
EP1433805B1 (fr) Dispersions des polyester résines amorphes et non saturées à base des certaines dicidol isomères
WO2010010075A1 (fr) Utilisation de 2-isopropyl-2-alkyl-1,3-propandiols pour la fabrication de polymères
DE19715382C1 (de) Wasserdispergierte, strahlenhärtbare Polyurethane
EP0610450B1 (fr) Vernis, procede pour sa fabrication et son utilisation
AT404733B (de) Verfahren zur herstellung von strahlungshärtbaren wasserverdünnbaren urethanharzen und deren verwendung
WO2006063897A1 (fr) Compositions durcissables aux rayonnements, procede pour leur production et leur utilisation
EP0883640B1 (fr) Nouveaux polyols polyester et leur utilisation comme constituants polyols dans des peintures polyurethane a deux composants
DE3935495A1 (de) Verfahren zur herstellung von ungesaettigten, urethanisierten polyesterharzen, die nach diesem verfahren erhaeltlichen polyesterharze und ihre verwendung als oder zur herstellung von beschichtungsmittel(n)
WO2006045662A1 (fr) Dispersions de polyesters contenant des groupes d'acide sulfonique, ces polyesters etant insatures et amorphes a base de certains dicidolisomeres
EP2848637A1 (fr) Dispersions de polyuréthane en base aqueuse comprenant des groupes d'hydroxyle, son procédé de fabrication et son utilisation dans des produits de revêtement
EP0871684A1 (fr) Liants a faible taux d'emission pour revetements
EP1654293B1 (fr) Composants de liant a fonction hydroxy
DE68903830T2 (de) Ester und urethan-harz von bis(hydroxyalkyl)-cycloalkan abgeschlossen durch ein vinylether.
EP0356847A2 (fr) Uréthanes allyliques et leur utilisation pour la production de vernis

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070703

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK DEGUSSA GMBH

17Q First examination report despatched

Effective date: 20071123

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK DEGUSSA GMBH

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20090603