EP3080181A1 - Composition de vernis sous forme de dispersion transparente non aqueuse - Google Patents

Composition de vernis sous forme de dispersion transparente non aqueuse

Info

Publication number
EP3080181A1
EP3080181A1 EP14809893.2A EP14809893A EP3080181A1 EP 3080181 A1 EP3080181 A1 EP 3080181A1 EP 14809893 A EP14809893 A EP 14809893A EP 3080181 A1 EP3080181 A1 EP 3080181A1
Authority
EP
European Patent Office
Prior art keywords
meth
polyurethane
acrylate
molecular weight
paint composition
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Withdrawn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
EP14809893.2A
Other languages
German (de)
English (en)
Inventor
Kirsten Siebertz
Klaus-Uwe Koch
Jorge Prieto
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.)
LEHMANN & VOSS & CO. KG
Original Assignee
Dritte Patentportfolio Beteiligungs GmbH and Co KG
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
Priority claimed from DE102013020915.3A external-priority patent/DE102013020915A1/de
Priority claimed from EP14160872.9A external-priority patent/EP2921512A1/fr
Application filed by Dritte Patentportfolio Beteiligungs GmbH and Co KG filed Critical Dritte Patentportfolio Beteiligungs GmbH and Co KG
Priority to EP14809893.2A priority Critical patent/EP3080181A1/fr
Publication of EP3080181A1 publication Critical patent/EP3080181A1/fr
Withdrawn legal-status Critical Current

Links

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
    • 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
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • 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
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents

Definitions

  • Lacquer composition in the form of a non-aqueous transparent dispersion in the form of a non-aqueous transparent dispersion
  • the invention relates to coating compositions in the form of nonaqueous transparent dispersions which are obtainable as reactive diluents, polyurethane (meth) acrylate particles which are obtainable by reacting a polyisocyanate with a polyol and a nucleophilically functionalized (meth) acrylic ester in the reactive diluent and have an average diameter of less than 40 nm, and contain an initiator.
  • Non-aqueous polyurethane dispersions have gained importance in recent years. They are used, inter alia, as a coating, adhesive and adhesive.
  • the documents DE 32 48 132, DE 35 13 248, EP 0 320 690 and EP 0 318 939 do not describe aqueous dispersions of polyurethanes for predominant use as coating compositions.
  • the solvent consists of a
  • Polyurethane particles forms.
  • the dispersion from DE 32 48 132 is known as
  • DE 10 2005 035 235 A1 describes nonaqueous transparent dispersions of polyurethane (meth) acrylate particles in a reactive diluent obtainable by reacting a polyisocyanate with at least one polyol and a nucleophilically functionalized (meth) acrylic ester in the reactive diluent and characterized in that the polyurethane (meth) acrylate particles have an average diameter of less than 40 nm.
  • DE 10 2005 035 235 A1 describes corresponding compositions for use as adhesive systems and castables and states that the solid-state cured dispersions have excellent impact strength properties and high tensile shear strength.
  • compositions described in this application especially for paint applications have insufficient properties, such as, among other things, an unfavorable viscosity. Accordingly, there is a need for compositions for paint applications that are completely transparent after cure and, at the same time, have an improved property profile in terms of their application properties, especially their adhesive strength, hardness and resistance to micro-scratches. These properties are particularly in the use of the compositions as a varnish of
  • lacquers should be as transparent as possible, on the other hand, however, the substrate or product underneath should be well shielded from external influences and protected, so that it is not damaged by everyday use.
  • Dispersion according to the invention as possible with components that are available easily and inexpensively.
  • a coating composition in the form of a nonaqueous transparent dispersion comprising: a reactive diluent
  • Polyurethane (meth) acrylate particles obtainable by reacting at least one polyisocyanate with at least one polyol and at least one nucleophilically functionalized (meth) acrylic ester in the
  • the present invention provides a
  • Paint composition in the form of a non-aqueous transparent dispersion which functionalized on the one hand with methacrylic acid esters
  • Polyurethane (meth) acrylate particles contains a reactive diluent and an initiator with which it is possible to functionalized
  • Polyurethane (meth) acrylate particles in the polymerization of the reactive diluent to covalently integrate into the matrix of the reactive diluent are transparent and remain transparent even after curing of the reactive diluent.
  • the coating composition according to the invention can be used directly as a lacquer, but it is also possible to add further additives and additives customary in lacquers to the composition, or to mix the composition with commercially available lacquer compositions and to use the formulation obtained therefrom as lacquer.
  • the paint of the invention has in the form of the cured dispersion, mediated by the contained polyurethane (meth) acrylate particles, a excellent adhesion to various substrates, excellent hardness and microcracking resistance.
  • a further advantage of the described dispersions is that they can be used over a longer period, i. h., At least two months, are stable at room temperature and therefore storable.
  • nucleophilic functionalized (meth) acrylic acid ester in the context of this invention denotes a (meth) acrylic acid ester which carries in its alcohol-derived radical a nucleophilic functional group which reacts with free isocyanate groups.
  • Preferred nucleophilic groups are hydroxy, amino and mercapto groups. Particularly preferred is a hydroxy group.
  • the most preferred nucleophilic functionalized (meth) acrylic esters having a hydroxy functionality are termed "hydroxy-functional
  • polyurethane (meth) acrylate in the context of this invention denotes a polyurethane whose free terminal isocyanate groups have been reacted with a nucleophilic functionalized (meth) acrylate ester.
  • the isocyanate groups react with the nucleophilic group of the nucleophilic functionalized (meth) acrylic ester, eg. As hydroxy, amino or mercapto groups, and there are formed terminal ethylenically unsaturated functionalities derived from (meth) acrylates.
  • (meth) acrylic acid refers herein to methacrylic acid, acrylic acid and mixtures of these acids.
  • nucleophilically functionalized (meth) acrylic acid esters react with the free isocyanate groups of the polyurethane, ie they "cap” them, they are also referred to as “capping reagents” or “capping reagents”.
  • reactive diluent is understood according to the invention to mean a substance which contains at least one ethylenic double bond.
  • Reactive diluent fulfills the following functions:
  • the reactive diluent serves as a liquid reaction medium for the reaction of polyisocyanate with at least one polyol and a nucleophilically functionalized (meth) acrylic ester.
  • the reactive diluent does not participate in the reaction mentioned.
  • the reactive diluent is the liquid dispersant for the formed functionalized
  • Polyurethane (meth) acrylate particles are embedded in the cured reactive diluent.
  • step 3 The product obtained after completion of step 3) is also referred to as "cured dispersion" in the context of this invention.
  • Dispersion takes place by copolymerization of the terminal, ethylenically unsaturated functionalities of the particles into the macromolecules of
  • polymerized matrix where "polymerized matrix” is to be understood as the polymerized reactive diluent.
  • the reactive diluent is not subject to any relevant restrictions, with the exception that it should as far as possible have no functional groups reactive toward polyisocyanates.
  • Suitable reactive diluents are listed, for example, in DE 10 2005 035 235 A1 in [0031].
  • the reactive diluent comprises a polyfunctional (meth) acrylate. It is preferred if this polyfunctional methacrylate is a difunctional (meth) acrylate.
  • Particularly suitable di (meth) acrylates in this context are the di (meth) acrylates of propanediol, butanediol, hexanediol, octanediol, nonanediol, decanediol and eicosanediol.
  • Further suitable difunctional (meth) acrylates are the di (meth) acrylate of ethylene glycol,
  • Diethylene glycol triethylene glycol, tetraethylene glycol, Dodekaethylenglykols, Tetradekaethylenglykols, propylene glycol, dipropylene glycol and
  • Suitable tri- or polyfunctional (meth) acrylates are for example the
  • Trimethylolpropane tri (meth) acrylate and the pentaerythritol tetra (meth) acrylate Trimethylolpropane tri (meth) acrylate and the pentaerythritol tetra (meth) acrylate.
  • polar monomers for example those having hydroxyl groups
  • monomers containing, for example, hydroxyl groups can react with isocyanates reactions. Therefore, such monomers can be added to the dispersion only after the polyaddition step.
  • the amount of such polar monomers is limited to the
  • Sensitivity to water swelling should not be unnecessarily increased.
  • polar, in particular hydroxyl-containing, monomers which are not covalently bound to the polyurethane (meth) acrylate particles and are therefore to be distinguished in their function from the nucleophilicly functionalized (meth) acrylic acid esters in amounts of not more than 0.1 to 20% by weight. -%, based on the total weight of the reactive diluent used.
  • the proportion of polyfunctional (meth) acrylates is at least 20% by weight, in particular
  • At least 30% by weight preferably at least 40% by weight, more preferably at least 50% by weight, even more preferably at least 70% by weight and most preferably at least 90% by weight, based on the weight of the
  • the reactive diluent consists exclusively of polyfunctional (meth) acrylates, more preferably exclusively of difunctional (meth) acrylates.
  • a reactive diluent based on (meth) acrylates may further
  • Containing comonomers which are copolymerizable with (meth) acrylates include, but are not limited to, vinyl esters, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, substituted styrenes having an alkyl substituent in the side chain such as ⁇ -methylstyrene and ⁇ -ethylstyrene, substituted styrenes having an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene , halogenated styrenes, such as monochlorostyrenes, dichlorostyrenes,
  • Tribromostyrenes or tetrabromostyrenes vinyl and isoprenyl ethers
  • Maleic acid derivatives such as maleic anhydride
  • Methylmaleic anhydride maleimide, methylmaleimide, phenylmaleimide and Cyclohexylmaleimide, and dienes such as 1,3-butadiene, divinylbenzene, diallyl phthalate and 1,4-butanediol divinyl ether.
  • the proportion of the abovementioned comonomers is 40% by weight of the
  • Reactive thinner limited, otherwise the mechanical properties of the cured dispersion can be adversely affected.
  • proportion of vinylaromatics here is limited to 30% by weight of the reactive diluent, since higher proportions can lead to segregation of the system and thus turbidity.
  • the reactive diluent is accordingly particularly preferred
  • polyisocyanates having three or more isocyanate groups may additionally be added.
  • proportion of polyisocyanates having three or more isocyanate groups can be the proportion of polyisocyanates having three or more isocyanate groups.
  • the proportion of polyisocyanates having three or more functionalities should not be greater than 10% by weight, preferably not more than 5% by weight, based on the total weight of polyisocyanates.
  • suitable polyisocyanates are:
  • Polyurethane (meth) acrylate particles to be included is an aliphatic isocyanate such as 4,4'- and 2,4'-methylenedicyclohexyl diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate (IPDI).
  • the polyisocyanate is a cycloaliphatic polyisocyanate, such as
  • Suitable polyisocyanates can also be obtained, for example, by reacting polyhydric alcohols with diisocyanates or by the polymerization of diisocyanates. Furthermore, polyisocyanates are also used
  • isocyanates can be used, which can be represented by reacting hexamethylene diisocyanates with small amounts of water. These products contain biuret groups. All mentioned isocyanates can be used individually or as a mixture.
  • the isocyanate is reacted with at least one polyol.
  • a polyol is understood in the context of the present
  • the polyol may have a uniform molecular weight or a statistical distribution of molecular weight.
  • the polyol is preferably a high molecular weight polyol having a statistical molecular weight distribution.
  • a "high molecular weight polyol” in the present invention means a polyol having two or more hydroxy groups, wherein the weight average molecular weight of the high molecular weight polyol is in the range of> 500 to about 20,000 g / mol. It is preferably in the range of> 500 to 15,000 g / mol,
  • polyether polyols Exemplary of high molecular weight polyols are the polyether polyols.
  • An example of polyether polyols are polyalkylene ether polyols of the structural formula
  • substituent R is hydrogen or a lower alkyl group of 1-5 carbon atoms, including mixed substituents, n
  • Polytetrahydrofuran poly (oxyethylene) glycols, poly (oxy-l, 2-propylene) glycols and the reaction products of ethylene glycol with a mixture of 1,2-propylene oxide, ethylene oxide and alkyl glycidyl ethers.
  • a particularly preferred polyol is polytetrahydrofuran. It is available, for example, from BASF under the trade names ®PTH F 650 or ®PTH F 2000. A very particularly preferred polyol in the context of the invention is ®PTH F 2000.
  • Polyether polyols having at least three hydroxyl functionalities can also be used.
  • at least three hydroxyl functionalities which can react with isocyanate groups it is possible to use, for example, alcohols which are at least three starting molecules
  • a preferred trifunctional polyol is a trifunctional polypropylene ether polyol of propylene oxide, ethylene oxide and glycerine. Such a polyol is marketed under the name Baycoll® BT 5035 by Bayer.
  • polyols also copolyester diols, d. H. linear copolyesters terminated by primary hydroxyl groups.
  • Their weight-average molecular weight, determined by means of GPC, is preferably 3000-5000 g / mol. They are obtainable by esterification of an organic polycarboxylic acid or a derivative thereof with organic polyols and / or an epoxide.
  • the polycarboxylic acids and polyols are aliphatic or aromatic dibasic acids and diols.
  • alkylene glycols such as
  • Ethylene glycol neopentyl glycol, or glycols such as bisphenol A,
  • Cyclohexanediol, cyclohexanedimethanol, caprolactone-derived diols e.g. As the reaction product of ⁇ -caprolactone and ethylene glycol, hydroxy-alkylated
  • Bisphenols polyether glycols such as poly (oxytetramethylene) glycol and the like used.
  • Polyols of higher functionality can also be used. They include, for example, trimethylolpropane, trimethylolethane, pentaerythritol, and higher molecular weight polyols, such as those made by oxyalkylation of low molecular weight polyols.
  • As the acid component in the copolyester diol it is preferable to use monomeric carboxylic acids or anhydrides having 2 to 36 carbon atoms per molecule. Usable acids are z. Phthalic acid, isophthalic acid,
  • the polyesters may contain small amounts of monobasic acids, such as. B.
  • Benzoic acid, stearic acid, acetic acid and oleic acid are also usable.
  • higher polycarboxylic acids such as trimellitic acid.
  • Medium-long copolyester diols preferred according to the invention are marketed by Degussa under the trade names DYNACOLL® 7380 and DYNACOLL® 7390.
  • copolyesters having a molecular weight Mw, determined by GPC, of about 5500 and a
  • Hydroxyl number from 18 to 24.
  • a corresponding polymer is available, for example, from Evonik under the trade name DYNACOLL® 7250.
  • reaction mixture is used to form the polyurethane (meth) acrylate particles in addition to a
  • Polyurethane (meth) acrylate particles obtainable by reacting a polyisocyanate with a high molecular weight polyol, a low molecular weight polyol and a hydroxyalkyl (meth) acrylic ester in the reactive diluent.
  • a "low molecular weight polyol” is understood according to the invention to mean a compound which has two or more hydroxyl functionalities and a molar mass of 50-500 g / mol, preferably 50-250 g / mol.
  • the molecular weight may be uniform or, in the case of a polymerization product, it may be randomly distributed, in the latter case the molecular weight being the weight average molecular weight.
  • Preferred as a low molecular weight polyol is one with a uniform
  • aliphatic diols having 2 to 18 carbon atoms such as. Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4- Butanediol, 1,2-hexanediol and 1,6-hexanediol, and the cycloaliphatic polyols, such as 1,2-cyclohexanediol and cyclohexanedimethanol, are particularly preferred.
  • the polyols with ether groups such as diethylene glycol and triethylene glycol and dipropylene glycol.
  • Exemplary of low molecular weight polyols having more than two hydroxy groups are trimethylolmethane
  • Trimethylolethane Trimethylolpropane, glycerol and pentaerythritol.
  • the most preferred low molecular weight polyols used are 1,4-butanediol and 1,3-propanediol. It is also possible to use low molecular weight polyols having a statistical molecular weight distribution.
  • a low molecular weight polyol having a statistical molecular weight distribution in principle, any polyol which is composed of the same monomeric units as the above-described high molecular weight polyols, but a
  • Molecular weight in the case of a low molecular weight polyol having a statistical molecular weight distribution will be predominantly in the vicinity of the upper limit of the previously defined range of 50-500 g / mol.
  • the low molecular weight polyol having a random distribution is preferably a trihydroxy-functional polyol, more preferably a trihydroxy-functional polyalkylene glycol, and most preferably a trihydroxy-functional polypropylene glycol.
  • Such trihydroxy-functional polyalkylene glycols suitably have a KOH number in the range from 140 to 600, and preferably in the range from 360 to 500.
  • a suitable trihydroxy-functional polyalkylene glycol is available, for example, as Desmophen 1380 BT from Bayer.
  • the molar ratio of the hydroxy groups of the low molecular weight trihydroxy-functional polyalkylene glycols is based on the
  • Polyalkylene glycols preferably 2% to 30% and particularly preferably 4 to 20%.
  • the polyol to be included in the polyurethane (meth) acrylate particles comprises at least one dihydroxy-functional and at least one trihydroxy-functional polyol.
  • the trihydroxy-functional polyol it is again preferred if this comprises a polyalkylene glycol, preferably a polypropylene glycol.
  • the polyol comprises a polyether diol having a weight average molecular weight of> 500 to 5000 g / mol and a polyether triol having a weight average molecular weight of> 50 to 500 g / mol, wherein the molar amount of OH Groups of the polyether triol having a weight average molecular weight of> 50 to 500 g / mol about 3 to 25%, preferably about 5 to 15%, the sum of the molar amount of the polyether diol having a weight average molecular weight of> 500 to 5000 g / mol and of the polyether triol having a weight average molecular weight of> 50 to 500 g / mol.
  • nucleophilic functionalized (meth) acrylic esters are hydroxy-functional (meth) acrylic esters.
  • a "hydroxy-functional (meth) acrylic acid ester” is understood according to the invention to mean a (meth) acrylic acid ester which, after esterification with (meth) acrylic acid, still carries at least one hydroxyl functionality in the residue derived from the alcohol. In other words, it is the ester of a (meth) acrylic acid and a diol or polyol, with diols being preferred.
  • hydroxyfunctional (meth) acrylic acid esters are the hydroxyalkyl (meth) acrylic acid esters.
  • Hydroxyalkyl (meth) acrylates which can be used according to the invention are esters of (meth) acrylic acid with dihydric, aliphatic alcohols. These compounds are well known in the art. You can, for example, by the reaction of
  • the oxirane compounds include, but are not limited to, ethylene oxide, propylene oxide, 1,2-butylene oxide and / or 2,3-butylene oxide, cyclohexene oxide, styrene oxide,
  • Epichlorohydrin and glycidyl ester These compounds can be used both individually and as a mixture.
  • the hydroxyalkyl (meth) acrylic acid esters can also contain substituents, such as, for example, phenyl radicals or amino groups.
  • Preferred hydroxyalkyl (meth) acrylic esters include 1-hydroxyethyl acrylate, 1-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate (H EA), 2-hydroxyethyl methacrylate (H EMA), 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate , 3-hydroxypropyl methacrylate, 6-hydroxyhexyl acrylate and 6-hydroxyhexyl methacrylate, 3-phenoxy-2-hydroxypropyl methacrylate, acrylic acid (4-hydroxybutyl ester), methacrylic acid (hydroxymethylamide), caprolactone hydroxyethyl methacrylate and caprolactone hydroxyethyl acrylate.
  • the hydroxyethyl methacrylates, the hydroxyethyl acrylates, 2-hydroxypropyl methacrylate and 2-hydroxypropyl acrylate are very particularly preferred. Most preferred are 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate.
  • hydroxyfunctional (meth) acrylic esters are the polyether methacrylates. These are substances which are obtained by esterification of a (meth) acrylic acid with a polyether polyol, preferably a polyether diol. Such polyether polyols have already been mentioned above in the mention of preferred polyols.
  • the hydroxyalkyl radical of the ester contains polyoxyalkylene groups, which may be both linear and branched, such as polyethylene oxide, polypropylene oxide and polytetramethylene oxide. These groups often have between 2 and 10 oxyalkylene units.
  • nucleophilically functionalized (meth) acrylic acid ester is chosen so that free isocyanate groups, which are still present after the polycondensation between polyisocyanate and polyol, are completely reacted.
  • the content of free isocyanate groups can be determined after the polycondensation. The determination of the content of free isocyanate groups can be carried out, for example, by infrared spectroscopic methods or by titration.
  • the polyurethane (meth) acrylate from which the particles of the dispersion according to the invention are synthesized generally has a weight-average molecular weight of from 3,000 to 600,000 g / mol, preferably from 3,000 to 500,000 g / mol, which with the aid of GPC determine is.
  • the polyurethane (meth) acrylate particles have an average diameter of less than 40 nm, whereby the desired transparency is achieved.
  • a mean particle diameter of less than 20 nm is achieved, more preferably less than 10 nm.
  • the specified diameters can be determined by means of light scattering. Corresponding methods are readily familiar to the person skilled in the art. A suitable device for determining the particle size is for example the
  • the solids content is to be understood as meaning the weight of the polyurethane (meth) acrylate particles, based on the weight of the entire dispersion.
  • the solids content is preferably at least 20% by weight. It is also preferable that the solid content is 80% by weight or less. Particularly preferred is a solids content of 30 to 50 wt .-% and most preferably 35 to 45 wt .-%, each based on the total weight of the dispersion.
  • any initiator with which a polymerization of the reactive diluent is possible can be used as initiator for the polymerization of the reactive diluent in the context of the present invention.
  • suitable initiators are, for example, peroxides and hydroxy peroxides, such as dibenzoyl peroxide, diacetyl peroxide and t-butyl hydroperoxide.
  • Another class of initiators are heat-activated initiators, especially azo initiators, such as azobisisobutyronitrile. If a peroxide is used as the initiator, its decomposition can be induced by means of promoters at low temperatures.
  • a particularly preferred promoter in this context is N, N-bis- (2-hydroxyethyl) -p-toluidine (DEPT).
  • the initiator used in the context of the present invention is preferably a UV-activatable photoinitiator.
  • Such photoinitiators typically distinguish between Norrish Type I and Norrish Type II photoinitiators.
  • Photoinitiators are those of the Norrish type I. Examples of such
  • Photoinitiators are the 2-hydroxy-2-methyl-1-phenyl-propane-1-one (available under the name Darocure® 1173 from Ciba) or the 1-hydroxycyclohexyl phenyl ketone, which is mixed with benzophenone (1: 1) as Irgacure® 500 from Ciba is available.
  • the amount of photoinitiator added is not substantially limited, but should be 10% by weight based on the amount of
  • Preferred levels of the photoinitiator are in the range of about 1 to 6 wt%, and more preferably about 2 to 4.5 wt%.
  • the coating composition according to the present invention may also contain suitable additives, in particular in the form of defoamers, solvents and / or film formers.
  • a suitable defoamer is, for example, Byk 141 from Byk. Defoamers are usually effective even in small amounts, so the content of
  • Defoamers in the paint composition of the invention should not exceed 3%.
  • the paint composition may contain a solvent, such as in particular butyl acetate.
  • the paint composition is not substantially limited, but it is desirable to use the solvent in amounts not exceeding 50% by weight based on the total weight of the paint composition.
  • the coating composition according to the invention is free of solvents.
  • the coating composition according to the invention contains from 20 to 50% by weight, in particular from 30 to 50% by weight.
  • Solvent preferably in the form of butyl acetate.
  • organic solvents may be desired, so that the
  • Processing parameters such. As viscosity, wet / dry film thickness and paint course can be adapted to user requirements.
  • the preferred application methods are z. As doctoring, rolling, casting, Vakuumat method, dipping, drumming, spraying (cup gun, airless, Airmix).
  • film formers are, for example
  • Cellulose derivatives are particularly suitable film formers. Particularly suitable film formers are cellulose esters,
  • the viscosity is between 50 and 500 mPa.s, more preferably about 80 to 300 mPa.s, and most preferably about 100 to 250 mPa.s. s.
  • the "paint expert" also speaks of the flow time in seconds which is determined using a flow cup in accordance with DIN 53211. According to DIN 53211, only one flow cup with a discharge nozzle of 4 mm diameter is standardized
  • the present invention also relates to a nonaqueous transparent dispersion of polyurethane (meth) acrylate particles in specific reactive diluents obtainable by reacting
  • the special reactive diluents include methyl methacrylate (MMA),
  • IBOA Isobornyl acrylate
  • H DDA hexanediol diacrylate
  • dipropylene glycol diacylate dipropylene glycol diacylate
  • tripropylene glycol diacrylate Such dispersions are transparent and remain transparent even after curing of the reactive diluent.
  • This dispersion can be cured in addition to a use as a paint for the formation of an adhesive bond or a casting. Except for a curing initiator no further substances have to be added.
  • the dispersion of the invention in conventional formulations of adhesive systems, paints, coatings or molding compounds, as described in part above, mix and then cure the formulation.
  • the polyisocyanates usable in the above aspect of the present invention include, in particular, tetramethylene diisocyanate (TM DI), tolylene diisocyanate (TDI) and isophorone diisocyanate (IPDI).
  • TM DI tetramethylene diisocyanate
  • TDI tolylene diisocyanate
  • IPDI isophorone diisocyanate
  • the polyurethane (meth) acrylate particles are available from tetramethylene diisocyanate as a polyisocyanate, a copolyester having a molecular weight of about 5,500 and a hydroxyl number of 18 to 24 and 1,4-butanediol as polyols, and from hydroxyethyl methacrylate as nucleophilically functionalized (meth) acrylate.
  • the reactive diluent in this case is preferably methyl methacrylate. It is very particularly preferred if the dispersion is based on polyurethane particles which consist of about 6% by weight of polymethylene diisocyanate, about 46% by weight of the
  • Copolyesters having a Mw of 5,500 and a hydroxyl number of 18 to 24, about 1 wt .-% 1,4-butanediol and about 4 wt .-% hydroxyethyl methacrylate are available, and 43 wt .-% methyl methacrylate as a reactive diluent based. in the
  • the nonaqueous transparent dispersion is based on polyurethane particles of tolylene diisocyanate as polyisocyanate,
  • (Meth) acrylic acid ester and isobornyl acrylate as a reactive diluent.
  • the dispersion is based on polyurethane particles n which comprise about 4% by weight of tolylene diisocyanate, about 27% by weight of the polytetrahydrofuran having an average molecular weight of about 2000 and about 4% by weight.
  • the nonaqueous transparent dispersion is based on polyurethane particles of isophorone diisocyanate as polyisocyanate, a mixture of polytetrahydrofuran having an average molecular weight of about 2000 and 1,4-butanediol as polyol and hydroxyethyl acrylate as nucleophilically functionalized (meth) acrylic ester and hexanediol diacrylate as a reactive diluent.
  • the dispersion is based on polyurethane particles which consist of about 12% by weight of isophorone diisocyanate, about 28% by weight of the polytetrahydrofuran having an average molecular weight of about 2000, about 2% by weight of 1,4-butanediol, and about 4% by weight of hydroxyethyl acrylate, and about 54% by weight of hexanediol diacrylate is a reactive diluent.
  • the polyol may optionally additionally contain trimethylolpropane or a trihydroxy-functional polypropylene glycol having a KOH number of about 385 mg KOH / g.
  • the molar amount of the OH groups from the trimethylolpropane or the trihydroxy-functional polypropylene glycol about 5 to 15% of the sum of the molar amount of OH groups of polytetrahydrofuran having an average molecular weight of about 2000 and the trimethyolpropane or the
  • the invention relates to a production method for the coating composition described above.
  • a polyisocyanate is reacted in a stirred tank with at least one polyol and a nucleophilically functionalized (meth) acrylic ester in a reactive diluent.
  • the coating composition according to the invention is then obtainable by adding to the reaction mixture, before or after polymerization of the polyisocyanate, an initiator.
  • a suitable process for the preparation of polyurethane (meth) acrylate particles is described, for example, in DE 10 2005 035 235 A1 in [0098] to [0112].
  • Another aspect of the present invention relates to a coated
  • Paint composition on the substrate and curing of the composition on the substrate is available.
  • the substrate is expediently glass, metal, preferably with a surface of aluminum, zinc or iron, and Plastics, preferably of PVC or polycarbonate. If, in the foregoing, metals having a surface of aluminum, zinc or iron are mentioned, this means that the surface, with the exception of unavoidable
  • Oxydations occurn of aluminum, zinc or iron, consisting essentially of elemental aluminum, zinc or iron.
  • Another aspect of the present invention relates to a method for
  • Preparation of a coated substrate comprising applying a coating composition as described above to a substrate and curing the coating composition on the substrate. It is preferred if the curing of the composition takes place under irradiation with UV light, which implies that the initiator used is a UV-light-activatable initiator.
  • the paint composition of the present invention has not only high transparency but also good transparency
  • Adhesive strength especially on substrates such as glass, metals or plastics, as well as a high hardness and resistance to micro-scratches.
  • Component II (cf., Tables 1 to 10 below) was added at 60 ° C. to component I in a dropping funnel heated to 60.degree
  • compositions of the various approaches are given in Tables 1 to 10 below.
  • the dispersions prepared according to the formulations from Tables 6 and 7 were clear, colorless liquids.
  • Comparative paint 1 based on Desmolux 2740 on different substrates was tested in accordance with DIN EN ISO 2409 (characteristic value ISO GT0 - GT5).
  • GT0 stands for very good adhesion
  • GT5 for complete delamination / poor adhesion.
  • Table 9 The results of these studies are shown in Table 9 below.
  • Paint 1 shows the best results. Comparative 1 based on Desmolux 2740 shows the worst results in this series of experiments. There are tendencies recognizable that with increasing polyol content (trifunctional), the adhesive strengths are slightly less favorable (paints 2 to 5). It is further shown that all paint formulations according to the invention, paint 1 to paint 5, exhibit improved adhesive strengths on all the substrates investigated in comparison with the commercially available product based on Desmolux 2724. The best bond strengths could be determined for the formulation Lack 1. All paints according to the invention, paint 1 to paint 5, show very high adhesive strengths on polycarbonate sheets and PVC films.
  • varnish 6 diol
  • comparison varnish 2 based on Desmolux 2740 were investigated.
  • the resistance to micro-scratches was determined according to the IH D factory standard W-466. This standard applies to furniture surfaces and serves to uniformly determine the resistance of the top lacquer layer to micro-scratches.
  • the test was carried out with a mini Martindale device. The Test specimens were subjected to 5 Lissajous movements (the Lissajous movement corresponds to 16 cycles of defined Reibtellerioloen according to methods A and B according to IH D-Werksnorm 466).
  • the Scotch-Brite friction materials 7447 (very fine) and 7448 (ultrafine) were used.
  • the test was carried out with a test force of 6 N according to method A (evaluation by determination of the gloss change). The investigations provided the results shown in Table 12.
  • Lacquer 6 and the comparison lacquer 2 based on Desmolux 2740 show a comparably low gloss change of 10.5% and 6.3%, respectively.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

La présente invention concerne une composition de vernis sous la forme d'une dispersion transparente non aqueuse, comprenant : un diluant réactif ; des particules de (méth)acrylate de polyuréthane qui peuvent être obtenues en faisant réagir un polyisocyanate avec un polyol et un (méth)acrylate à fonctionnalité nucléophile dans le diluant réactif pour former des particules de (méth)acrylate de polyuréthane ayant un diamètre moyen inférieur à 40 nm ; et un amorceur. Après durcissement, les compositions de vernis correspondantes se distinguent par des propriétés particulièrement favorables, notamment en termes d'adhérence, de dureté et de résistance aux microrayures, et elles sont donc supérieures dans bien des cas aux vernis classiques préparés sans nanoparticules de (méth)acrylate de polyuréthane.
EP14809893.2A 2013-12-12 2014-12-12 Composition de vernis sous forme de dispersion transparente non aqueuse Withdrawn EP3080181A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14809893.2A EP3080181A1 (fr) 2013-12-12 2014-12-12 Composition de vernis sous forme de dispersion transparente non aqueuse

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102013020915.3A DE102013020915A1 (de) 2013-12-12 2013-12-12 Nichwässrige Dispersion von Polyurethan(meth)acrylatpartikeln in Reaktivverdünner
EP14160872.9A EP2921512A1 (fr) 2014-03-20 2014-03-20 Composition de laque sous forme de dispersion transparente non aqueuse
EP14809893.2A EP3080181A1 (fr) 2013-12-12 2014-12-12 Composition de vernis sous forme de dispersion transparente non aqueuse
PCT/EP2014/077510 WO2015086796A1 (fr) 2013-12-12 2014-12-12 Composition de vernis sous forme de dispersion transparente non aqueuse

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EP3080181A1 true EP3080181A1 (fr) 2016-10-19

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US (1) US20160297991A1 (fr)
EP (1) EP3080181A1 (fr)
JP (1) JP2017508015A (fr)
KR (1) KR20160106601A (fr)
CN (1) CN105960423A (fr)
CA (1) CA2932234A1 (fr)
MX (1) MX2016007256A (fr)
WO (1) WO2015086796A1 (fr)

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EP3115387A1 (fr) * 2015-07-08 2017-01-11 Universiteit Gent Nouveaux matériaux à base d'uréthane, dérivés, leurs procédés de préparation et leurs utilisations
EP3320008B1 (fr) * 2015-07-08 2023-12-06 Universiteit Gent Nouveaux matériaux à base d'uréthane, dérivés, leurs procédés de préparation et leurs utilisations
DE102019113331A1 (de) * 2019-05-20 2020-11-26 Brillux Gmbh & Co. Kg Verfahren zum Beschichten einer Oberfläche
KR102231355B1 (ko) * 2019-09-19 2021-03-23 부경대학교 산학협력단 고분자 나노복합재, 및 이의 제조방법

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US4425468A (en) 1981-12-31 1984-01-10 Ppg Industries, Inc. Polyurea-polyurethane acrylate polymer dispersions
US4569966A (en) 1984-04-19 1986-02-11 Ppg Industries, Inc. Polymeric microparticles
US4783502A (en) 1987-12-03 1988-11-08 Ppg Industries, Inc. Stable nonaqueous polyurethane microparticle dispersion
US4833177A (en) 1987-12-03 1989-05-23 Ppg Industries, Inc. Method for preparing stably dispersed nonaqueous microparticle dispersion
DE19736083A1 (de) * 1997-08-20 1999-02-25 Basf Coatings Ag Mehrschichtlackierungen und Verfahren zu deren Herstellung
DE102005035235A1 (de) 2005-07-25 2007-02-01 Fachhochschule Gelsenkirchen Nichtwässrige Dispersion von Polyurethan(meth)acrylatpartikeln in Reaktivverdünner
EP2169677A4 (fr) * 2007-06-29 2011-01-05 Dainippon Ink & Chemicals Composition pouvant être durcie par ultraviolets pour une couche d'émission de lumière et disque optique
CN102482145B (zh) * 2009-12-17 2016-08-03 帝斯曼知识产权资产管理有限公司 可辐射固化光纤涂料组合物的led固化
KR20120111728A (ko) * 2009-12-28 2012-10-10 다이니폰 인사츠 가부시키가이샤 코팅제 조성물 및 이것을 사용한 시트
JP2012030586A (ja) * 2010-07-05 2012-02-16 Nitto Denko Corp 多層シートの製造方法および多層シート
DE102012007823A1 (de) * 2012-04-16 2013-10-17 Dritte Patentportfolio Beteiligungsgesellschaft Mbh & Co.Kg Polymerisate, die durch emulsionspolymerisation von funktionalisierten polyurethan-nanopartikeln und radikalisch härtbaren monomeren herstellbar sind, ein verfahren zu deren herstellung sowie deren verwendung

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MX2016007256A (es) 2016-09-07
CA2932234A1 (fr) 2015-06-18
KR20160106601A (ko) 2016-09-12
WO2015086796A1 (fr) 2015-06-18
US20160297991A1 (en) 2016-10-13
JP2017508015A (ja) 2017-03-23
CN105960423A (zh) 2016-09-21

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