EP2951251A1 - Composition de revêtement séchant par rayonnement ultraviolet - Google Patents

Composition de revêtement séchant par rayonnement ultraviolet

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Publication number
EP2951251A1
EP2951251A1 EP14704099.2A EP14704099A EP2951251A1 EP 2951251 A1 EP2951251 A1 EP 2951251A1 EP 14704099 A EP14704099 A EP 14704099A EP 2951251 A1 EP2951251 A1 EP 2951251A1
Authority
EP
European Patent Office
Prior art keywords
substrate
absorber
alkyl
formula
coating 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Withdrawn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
EP14704099.2A
Other languages
German (de)
English (en)
Inventor
Serguei Kostromine
Frauke KÜHN
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.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
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 Covestro Deutschland AG filed Critical Covestro Deutschland AG
Priority to EP14704099.2A priority Critical patent/EP2951251A1/fr
Publication of EP2951251A1 publication Critical patent/EP2951251A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • C08G18/28—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
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
    • 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
    • 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
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines

Definitions

  • the present invention relates to a coating composition
  • a coating composition comprising:
  • polycarbonate has the disadvantage that it is not inherently UV-stable.
  • the sensitivity curve of bisphenol A polycarbonate has the highest sensitivity between 320 nm and 330 nm.
  • UV stabilizers which are known to be used in coatings are UV absorbers, such as 2-hydroxybenzophenones, 2- (2-hydroxyphenyl) benzotriazoles, 2- (2-hydroxyphenyl) -1,3,5-triazines, 2-cyanoacrylates and oxalanilides, and radical scavengers of the HALS type (hindered amine light stabilizer).
  • UV absorbers such as 2-hydroxybenzophenones, 2- (2-hydroxyphenyl) benzotriazoles, 2- (2-hydroxyphenyl) -1,3,5-triazines, 2-cyanoacrylates and oxalanilides
  • radical scavengers of the HALS type hinderethoxyse
  • the UV protection becomes weaker when the UV absorber diffuses out of the binder. Furthermore, when the binder network is disturbed, especially when large amounts of fillers or additives are used, the mechanical properties and the stability to attacking materials change.
  • WO 2010/130349 A1 describes a multilayer structure in which the first layer consists of a UV-curing protective layer with silica nanoparticles and the second layer is a thermoplastic substrate.
  • the coating has a high abrasion resistance. Weathering data is not shown. Only non-reactive UV absorbers that can not bind to the matrix are used.
  • WO 2011/040541 A1 describes an optical laminate comprising a light-transmitting substrate and a scratch-resistant coating on the light-transmitting substrate.
  • WO 2011/006552 describes a process for coating in particular transparent polycarbonate substrates, in which a transparent coating composition comprising at least one radiation-curing binder (A) and / or reactive diluent (C), nanoparticles (B), optionally solvent and at least one light stabilizer (L) , is applied to a polycarbonate substrate, characterized in that the coating composition contains at least one light stabilizer (L) containing on average per molecule at least one bound via a urethane group ethylenically unsaturated group and the coating agent.
  • a transparent coating composition comprising at least one radiation-curing binder (A) and / or reactive diluent (C), nanoparticles (B), optionally solvent and at least one light stabilizer (L)
  • the coating composition contains at least one light stabilizer (L) containing on average per molecule at least one bound via a urethane group ethylenically unsaturated group and the coating agent.
  • WO 2000/66675 also describes in a large number of UV absorbers UV absorbers which are covered by the formula (Ib) and their use in coating compositions.
  • the combination of UV absorber and non-installable HALS are not in this document
  • the scratch-resistant layer is prepared by curing a composition for a scratch-resistant layer containing a polyfunctional UV-curable (meth) acrylic acid binder, a UV absorber and a photopolymerization initiator with ultraviolet light.
  • UV absorbers various hydroxyphenylbenzotriazoles and triazines and their copolymers with (meth) acrylates are described.
  • UV absorbers containing a (meth) acrylate group are used for copolymerization to increase the molecular weight of the molecule.
  • the hardening energies used are very small (in the range of 250 mJ / cm 2 ), which leads to a hardness gradient in the lacquer layer and to a gradient in the degree of polymerization along the layer thickness. This is in contrast to the systems described in this application, which are cured with significantly higher energy to achieve complete curing of the entire layer thickness.
  • UV absorbers with polymerizable groups are also mentioned, but the adhesive composition is a physical mixture of the components that cures without chemical reaction between UV absorber and matrix.
  • No. 5,869,588 describes polymeric components which are obtained by homopolymerization of UV absorbers with unsaturated groups or by copolymerization of these UV absorbers with ethylenically unsaturated monomers.
  • the UV absorber should not migrate out of the coating when exposed to moisture and heat.
  • the UV absorber in the component matrix should have a very good solubility or dispersibility, so that optically transparent parts are present after a coating.
  • a coating composition comprising:
  • the organic UV absorber C) is an absorber of the general formula (Ia):
  • R is a hydrogen or a methyl radical
  • T is a nucleus of the commercially available aliphatic and cycloaliphatic polyisocyanates T (NCO) m having cyclic isocyanurate, uretdione, iminooxadiazinedione or oxadiazinetrione structures, as well as having branched biuret structures in the case of the cycloaliphatic polyisocyanates.
  • NCO aliphatic and cycloaliphatic polyisocyanates
  • A is an optionally substituted linear or branched alkylene having preferably 1 to 20, more preferably 4 to 18, in particular 6 to 12 carbon atoms, wherein the carbon chain by oxygen, carboxyl, nitrogen, sulfur, phosphorus and / or silicon, preferably oxygen and / or Carboxyl, may be interrupted, and x represents the average molar fraction of the attached UV absorber residue and is less than m. Preferably, x is equal to or less than 1.
  • the compounds of the formula (Ia) according to the invention preferably have a UV absorption maximum between 300-340 nm.
  • a in the compounds of the general formula (Ia) is preferably an optionally substituted linear or branched linker, a chain of at least 4 atoms being selected between the O atom of the aromatic nucleus of the UV absorber and the O atom of the urethane group consists of carbon, oxygen, nitrogen, sulfur, phosphorus and / or silicon in the chain,
  • R 'and R " is H, Ci-20-alkyl, C4-i2-cycloalkyl, optionally substituted by Ci-12-alkyl, Ci-12-alkoxy, CN and / or halogen-substituted C6-i2-aryl or optionally by C C3-i2-heteroaryl substituted by 12-alkyl, Ci-12-alkoxy, CN and / or halogen,
  • X is branched or unbranched Ci-20-alkyl and
  • R is H or CH 3 .
  • compositions for the preparation of the composition Component A.
  • R 1 and R 2 independently of one another are H or C 1 to C 30 -alkyl, preferably H, methyl or ethyl and
  • R 3 in the case of polymer precursors according to component A.1 is an n-valent organic radical which consists of urethane or ester bonds linked aliphatic hydrocarbon units, or
  • R 3 in the case of polymer precursors according to component A.2 is an n-valent organic radical, preferably having 1 to 30 carbon atoms.
  • Suitable oligomers according to component A.1 belonging to the class of aliphatic urethane acrylates or polyester acrylates and their use as paint binders are known and are described in Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Vol. 2 , 1991, SITA Technology, London (PKT: Oldring (Ed.) On p.73-123 (Urethane Acrylates) and p.123-135 (Polyester Acrylates), respectively.
  • aliphatic urethane acrylates such as Ebecryl ® 4858, Ebecryl ® 284, Ebecryl ® 265, Ebecryl ® 264 (manufacturer in each Cytec Surface Specialties), Craynor ® 925 from Cray Valley, Viaktin ® 6160 from Vianova Resin, Desmolux ® U 100 from Bayer MaterialScience AG, Photomer ® 6891 from Cognis or in reactive diluents dissolved aliphatic urethane acrylates such as Laromer ® 8987 (70% in hexanediol diacrylate) from BASF AG, Desmolux ® U 680 H (80% in hexanediol diacrylate) from Bayer material Science AG, Craynor ® 945B85 (85% in hexanediol diacrylate) and Craynor ® 963B80 (80% in he
  • Suitable in the context of the invention are, for example, methanediol diacrylate, 1,2-ethanediol diacrylate, 1,3-propanediol diacrylate, 1,2-propanediol diacrylate, glycerol triacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, 1,2,4-butanetriol triacrylate, 1 , 5-pentanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, 1,6-hexanediol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, tricyclodecanedimethanol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate,
  • Particular preference is given to using 1,6-hexanediol diacrylate, tricyclodecanedimethanol diacrylate and methacrylate derivatives thereof, in particular as a mixture with component A.1.
  • component A.I comprises an unsaturated aliphatic urethane acrylate (preferably dissolved in reactive diluent), particularly preferably an unsaturated aliphatic urethane triacrylate.
  • Component B comprises finely divided inorganic compounds, these preferably consisting of at least one polar compound of one or more metals of the 1st to 5th main group or 1st to 8th subgroup of the Periodic Table, preferably the 2nd to 5th main group or 4th to 8th Subgroup, particularly preferably from 3rd to 5th main group or 4th to 8th subgroup, or from compounds of these metals with at least one element selected from oxygen, hydrogen, sulfur, phosphorus, boron, carbon, nitrogen or silicon.
  • Examples of preferred compounds are oxides, hydroxides, hydrous oxides, sulfates, sulfites, sulfides, carbonates, carbides, nitrates, nitrites, nitrides, borates, silicates, phosphates, hydrides, phosphites or phosphonates.
  • the finely divided inorganic compounds of oxides, phosphates, hydroxides preferably from T1O2, S1O2, SnO 2, ZnO, ZnS, ZrO 2, Al 2 O 3, AIO (OH), boehmite, aluminum phosphates, further TiN, WC, Fe 2 O 3, iron oxides, NaSO i, Vanadium oxides, zinc borate, silicates such as Al silicates, Mg silicates, one-, two-, three-dimensional silicates. Mixtures and doped compounds are also useful. Particularly preferred are hydrated aluminas (eg boehmite) and silica. Particularly preferred is silica.
  • the finely divided inorganic compounds in the sense according to the invention have an average particle size (d.sub.50 value) of from 1 to 200 nm, preferably from 5 to 50 nm, particularly preferably from 7 to 40 nm.
  • the finely divided inorganic compounds have a narrow particle size distribution with a ((ds> o - dio) / dso) value of the distribution of less than or equal to 2, more preferably from 0.2 to 1.0.
  • the particle size is determined by analytical ultracentrifugation, whereby 90%, 10% and 10%, respectively, is the mean value of the integral mass distribution of the particle size. The use of analytical ultracentrifugation for particle sizing is described in H.G. Müller Progr. Colloid Polym. Be. 2004, 127, pages 9-13.
  • the surface of these finely divided inorganic compounds may be modified by means of alkoxysilane or alkylsilane compounds.
  • the finely divided inorganic compound is used as a dispersion in at least one component selected from the group consisting of A) and F). Preference is given to finely divided inorganic compounds which are dispersible agglomerate-free in the paint formulation.
  • the UV absorber of component C will be further discussed in connection with preferred embodiments. In general, it can be stated that upon photochemical curing of the coating composition, the UV absorber is incorporated into the polymer matrix.
  • T is preferably an isocyanurate based on hexamethylene diisocyanate (HDI).
  • Q is preferably CH 2 -CH 2 (ethylene).
  • the coating composition according to the invention in the formula (Ia) for the UV absorber C) A is preferably C (CH 3 ) -CO-O-CH 2 -CR 4 R 5 -CH 2 "where R 4 and R 5 independently of one another are alkyl having 1 to 6 carbon atoms, preferably methyl and / or ethyl.
  • X is CH (CH 3 ).
  • each r is 1.
  • each r is 1.
  • each r is 1 , R 2 and R 3 for H.
  • the UV absorber C) of the formula (Ib) is preferably selected from the following compounds:
  • These compounds can be, for example, by transesterification of commercially available precursors such as Tinuvin ® 479 (s. Below) obtained with (meth) acrylic acid.
  • Urethane acrylate containing UV absorber according to formula (Ia) can be prepared, for example, as follows: a) reaction of a compound of the general formula:
  • X is branched or unbranched Ci-20-alkyl and R 'is branched or unbranched Ci-20-alkyl, C4-i2-cycloalkyl or optionally by Ci-12-alkyl, Ci-12-alkoxy, CN and / or halogen substituted C6-i2-aryl with an at least difunctional alcohol;
  • step a) Reaction of the product obtained in step a) with bi) an aliphatic or cycloaliphatic, isocyanate group-containing urethane acrylate having cyclic isocyanurate, uretdione, iminooxadiazinedione or oxadiazinetrione structures or, in the case of a cycloaliphatic urethane acrylate, may further have branched biuret structures and / or with bii) an aliphatic or cycloaliphatic polyisocyanate containing isocyanate groups which has cyclic isocyanurate, uretdione, iminooxadiazinedione or oxadiazinetrione structures or, in the case of a cycloaliphatic polyisocyanate, may further have branched biuret structures, wherein the reaction in step b), further in the presence of a hydroxyalkyl (meth) acrylate and / or after the reaction in step
  • (Z Cl to C18 alkylene, preferably Cl to C12 alkylene, for example methylene, ethylene, propylene or octylene.
  • a further embodiment of the production process is that instead of the polyisocyanates T (NCO) m, the NCO-containing urethane acrylates (formula V):
  • the substance of the formula IV is added to the polyisocyanate in the form of a solution in a further reagent of the process, such as hydroxyalkyl (meth) acrylate.
  • the remaining amount of the hydroxyalkyl (meth) acrylate is added later in a second step of the reaction.
  • the substance of formula IV is added to the polyisocyanate in the form of a solution in NCO-neutral solvent.
  • the hydroxyalkyl (meth) acrylate then comes in the whole amount for reaction later as a second step.
  • the fact that the reaction NCO group with OH group proceeds according to the invention without catalyst, allows the use of tertiary alcohols, such as. Diacetone alcohol, as a solvent (particularly advantageous) for this synthesis.
  • the substance of formula IV reacts in the form of a melt with the polyisocyanate.
  • the hydroxyalkyl (meth) acrylate then reacts later as a second step in the whole amount.
  • Component D in the sense of the invention are so-called HALS systems (hindered amine light stabilizers).
  • HALS system of the present invention is an amine compound which is sterically hindered, generally being liquid or solid piperidine derivatives of the general structure as in formula (IV). in which
  • Z a divalent functional group such as, for example, and preferably C (0) 0, NH or NHCO,
  • R 16 is H or Ci-C 20 alkyl.
  • Sterically hindered amines act as radical scavengers to scavenge the radicals that result from polymer degradation. They are not installable, ie they contain no reactive groups that can react with component A.
  • a general overview of various types of HALS is given in T. Bolle: Lackadditive, J. Bielemann, eds.:, Wiley-VCH, Weinheim (1998) and in A. Valet: light stabilizer for paints, Vincentz Verlag, Hannover (1996) given.
  • Preferred HALS can be found in EP1308084A and DE60307122A.
  • Component E in the sense of the invention are preferably all those leveling agents which allow both a good wetting of the paint formulation on the surface of the second layer, as well as a visually appealing surface of the first layer formed during curing of the paint formulation.
  • An overview of common leveling agents is provided by Janos Hajas "Leveling Additives” in Additives in Coatings, Johan Bieleman (Edt), Wiley-VCH Verlag GmbH, Weinheim 2000, pages 164 to 179.
  • Surfactants for example polydimethylsiloxanes, can be used as leveling agents and the leveling agent BYK ® is preferably 300 (silicone-based surface additive from BYK Chemie GmbH).
  • Component F in the sense of the invention are solvents or solvent mixtures, which must be compatible with the second layer to the extent, as well as to the extent dispersing, applying and venting the paint formulation must allow that after UV curing of the paint formulation to the actual protective layer, a multi-layer product high transparency and low turbidity is obtained.
  • solvents or solvent mixtures which must be compatible with the second layer to the extent, as well as to the extent dispersing, applying and venting the paint formulation must allow that after UV curing of the paint formulation to the actual protective layer, a multi-layer product high transparency and low turbidity is obtained.
  • These may be, for example and preferably, alkanes, alcohols, esters, ketones or mixtures of the above. Particular preference is given to using alcohols (with the exception of methanol), ethyl acetate and butanone.
  • solvents or solvent mixtures selected from at least one of the group consisting of diacetone alcohol (CH 3) 2 C (OH) CH 2 C (0O) CH 3, ethyl acetate, methoxypropanol and butanone.
  • the composition contains initiators for curing. Preference is given to UV initiators (photoinitiators).
  • Suitable UV initiators preferably have a high photochemical reactivity and an absorption band in the near UV range (> 300 nm and preferably> 350 nm).
  • Suitable photoinitiators are preferably those selected from the group of acylphosphine oxide derivatives and ⁇ -aminoalkylphenone derivatives.
  • acylphosphine oxide derivatives Preferably bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure® 819 from Ciba Specialty Chemicals), (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (Lucirin® TPO Solid by BASF AG), bis (2,6-dimethylbenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide, benzoylphosphonic acid bis (2,6- dimethylphenyl) ester (Lucirin® 8728 by BASF AG), ethyl-2,4,6-trimethylbenzoylphenylphosphin
  • mixtures of these photoinitiators with other known photoinitiators can be used; for example, a-hydroxyalkylphenone or phenylacetophenone.
  • component F is such that an experimentally determined solids content of 20 to 50 wt .-%, preferably 30 to 40 wt .-% for the mixture of components A, B and F results.
  • a further subject of the present invention is a process for coating a substrate, comprising the steps of: applying a coating composition according to the invention to a substrate
  • the composition is applied to the surface of the substrate by flooding, dipping, spraying, rolling or spin coating and then at room temperature and / or elevated temperature (preferably at 20-200 ° C, more preferably at 40-120 ° C). flashed.
  • the surface of the substrate may be pretreated by purification or activation.
  • the curing of the protective layer by means of UV light preferably a mercury vapor lamp doped with iron, or a pure mercury vapor lamp or a doped with gallium used as the UV light source.
  • UV light preferably a mercury vapor lamp doped with iron, or a pure mercury vapor lamp or a doped with gallium used as the UV light source.
  • the dose according to the invention of at least 2 J / cm 2 achieves through-hardening of the entire layer of the coating agent and incorporation of the UV absorber into the polymer matrix that forms.
  • a preferred dose is in the range of 3 to 6 J / cm 2 .
  • the UV dose can be determined using a UV-4C SD measuring instrument from UV-Technik Meyer GmbH, the dose being the sum of the radiated energy in the range from 230 to 445 nm.
  • the substrate is a thermoplastic substrate. In a further embodiment of the method according to the invention, the substrate is a polycarbonate substrate.
  • Thermoplastic polymers of the substrate in the sense of the invention are polycarbonate, polyester carbonate, polyesters (such as polyalkylene terephthalate), polymethyl methacrylate polyphenylene ethers, graft copolymers (such as ABS) and mixtures thereof.
  • the second layer is preferably polycarbonate, in particular homopolycarbonate, copolycarbonate and / or thermoplastic polyester carbonate.
  • M w average molecular weights of from 18,000 to 40,000, preferably from 22,000 to 36,000 and in particular from 24,000 to 33,000, determined by measuring the relative solution viscosity in dichloromethane or mixtures of equal amounts by weight of phenol / o-dichlorobenzene calibrated by light scattering.
  • the polycarbonates according to the invention and optionally further contained stabilizers, heat stabilizers, antistatic agents and pigments are added in the usual amounts; if appropriate, the demolding behavior and / or the flow behavior can be improved, even by adding external mold release agents and / or flow agents (for example alkyl- and aryl phosphites, -phosphates, -phosphines, -noledemolecular carboxylic acid esters, halogen compounds, salts, chalk, quartz powder, Glass and carbon fibers, pigments and their combination).
  • Such compounds are z.
  • WO 99/55772 pages 15-25, EP 1 308 084 and in the corresponding chapters of the "Plastics Additives Handbook", ed. Hans Zweifel, 5 th Edition 2000, Hanser Publishers, Kunststoff.
  • polycarbonates For the production of polycarbonates, reference is made by way of example to WO 2004/063249 A1, WO 2001/05866 A1, WO 2000/105867, US Pat. No. 5,340,905, US Pat. No. 5,097,002, US Pat. No. 5,717,057 and the literature cited therein.
  • the polycarbonates are preferably prepared by the phase boundary process or the melt transesterification process and will be described below by way of example using the phase boundary process.
  • Preferred compounds to be used as starting compounds are bisphenols of the general formula (V) HO-R-OH (V), wherein R is a divalent organic radical of 6 to 30 carbon atoms containing one or more aromatic groups.
  • Examples of such compounds are bisphenols belonging to the group of dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, indanebisphenols, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) ketones and a, a'-bis (hydroxyphenyl) diisopropylbenzenes belong.
  • bisphenols belonging to the aforementioned linking groups are bisphenol-A, tetraalkylbisphenol-A, 4,4- (meta-phenylenediisopropyl) diphenol (bisphenol M), 4,4- (para-phenylenediisopropyl) diphenol, 1, 1 - Bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BP-TMC) and optionally mixtures thereof.
  • the bisphenol compounds to be used according to the invention are preferably reacted with carbonic acid compounds, in particular phosgene, or with diphenyl carbonate or dimethyl carbonate during the melt transesterification process.
  • Polyestercarbonates are preferably obtained by reacting the abovementioned bisphenols, at least one aromatic dicarboxylic acid and optionally carbonic acid equivalents.
  • Suitable aromatic dicarboxylic acids are, for example, phthalic acid, terephthalic acid, isophthalic acid, 3,3'- or 4,4'-diphenyldicarboxylic acid and benzophenone dicarboxylic acids.
  • a portion, up to 80 mole%, preferably from 20 to 50 mole%, of the carbonate groups in the polycarbonates may be replaced by aromatic dicarboxylic acid ester groups.
  • Inert organic solvents used in the interfacial process include, for example, dichloromethane, the various dichloroethanes and chloropropane compounds, tetrachloromethane, trichloromethane, chlorobenzene and chlorotoluene, preferably chlorobenzene or dichloromethane or mixtures of dichloromethane and chlorobenzene.
  • the interfacial reaction can be accelerated by catalysts such as tertiary amines, in particular N-alkylpiperidines or onium salts.
  • catalysts such as tertiary amines, in particular N-alkylpiperidines or onium salts.
  • Tributylamine, triethylamine and N-ethylpiperidine are preferably used.
  • the catalysts mentioned in DE-A 4 238 123 are preferably used.
  • the polycarbonates can be deliberately and controlled branched by the use of small amounts of branching.
  • Some suitable branching agents are: phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2; 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptane; 1, 3,5-tri- (4-hydroxyphenyl) benzene; 1,1,1-tris (4-hydroxyphenyl) ethane; Tri- (4-hydroxyphenyl) -phenylmethane; 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] -propane; 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol; 2,6-bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol; 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) - propane; Hexa- (4- (4-hydroxypheny
  • the optionally used 0.05 to 2 mol%, based on diphenols, of branching agents or mixtures of the branching agents can be used together with the diphenols but can also be added at a later stage of the synthesis.
  • the chain terminators used are preferably phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof in amounts of 1 to 20 mol%, preferably 2 to 10 mol% per mol of bisphenol. Preference is given to phenol, 4-tert-butylphenol or cumylphenol.
  • Chain terminators and branching agents may be added separately or together with the bisphenol to the syntheses.
  • polycarbonates for the second layer of the multilayer product according to the invention are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the copolycarbonates based on Both monomers bisphenol A and l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • the homopolycarbonate based on bisphenol A is particularly preferred.
  • the polycarbonate may contain stabilizers. Suitable stabilizers are, for example, phosphines, phosphites or Si-containing stabilizers and further compounds described in EP-A 0 500 496. Examples which may be mentioned are triphenyl phosphites, diphenylalkyl phosphites, phenyldialkyl phosphites, tris (nonylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite and triaryl phosphite.
  • phosphines phosphites or Si-containing stabilizers and further compounds described in EP-A 0 500 496. Examples which may be mentioned are triphenyl phosphites, diphenylalkyl phosphites, phenyldialkyl phosphites, tris (nonylphenyl) phosphite
  • the polycarbonate-containing substrate of the multi-layered product according to the invention may contain from 0.01 to 0.5% by weight of the esters or partial esters of monohydric to hexahydric alcohols, in particular glycerol, pentaerythritol or guerbet alcohols.
  • Monohydric alcohols include stearyl alcohol, palmityl alcohol and Guerbet alcohols.
  • a dihydric alcohol is glycol.
  • a trivalent alcohol is, for example, glycerin.
  • tetrahydric alcohols include pentaerythritol and mesoerythritol.
  • pentavalent alcohols are arabitol, ribitol and xylitol.
  • Hexahydric alcohols include mannitol, glucitol (sorbitol) and dulcitol.
  • the esters are preferably the monoesters, diesters, triesters, tetraesters, pentaesters and hexaesters or mixtures thereof, in particular random mixtures of saturated, aliphatic Cio to C36 monocarboxylic acids and optionally hydroxy-monocarboxylic acids, preferably with saturated, aliphatic C14 to C32 monocarboxylic acids and optionally hydroxy-monocarboxylic acids.
  • the commercially available fatty acid esters in particular of pentaerythritol and of glycerol, may contain ⁇ 60% of different partial esters as a result of the preparation.
  • Saturated, aliphatic monocarboxylic acids having 10 to 36 carbon atoms are, for example, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid and montan acids.
  • Preferred saturated, aliphatic monocarboxylic acids having 14 to 22 carbon atoms are, for example, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, arachic acid and behenic acid.
  • saturated aliphatic monocarboxylic acids such as palmitic acid, stearic acid and hydroxystearic acid.
  • the saturated, aliphatic Cio to C36-carboxylic acids and the fatty acid esters are as such either known from the literature or can be prepared by literature methods.
  • pentaerythritol fatty acid esters are those of the particularly preferred monocarboxylic acids mentioned above.
  • Particularly preferred are esters of pentaerythritol and glycerol with stearic acid and palmitic acid.
  • the invention also includes a multi-layer structure comprising the substrate A and a protective layer B prepared by curing the composition according to the invention.
  • further layers are possible, either on the cured composition or on the substrate before the composition according to the invention is applied.
  • further layers are possible with a layer sequence BAB.
  • the layers B may be identical or different according to the composition described.
  • the multilayer products according to the invention or the thermoplastic polymers used for the preparation may contain organic dyes, inorganic color pigments, fluorescent dyes and particularly preferably optical brighteners. Further objects of the invention are the production of the coated products as well as the products constructed from the multi-layered products. Likewise provided by the present invention is the use of said multi-layered products, especially for outdoor applications with permanently high demands on the visual impression, such as the glazing.
  • the invention also relates, in particular, to multilayer products which contain as substrate a plastics molding, which is preferably made of thermoplastic polymer by means of injection molding or extrusion, and which are coated with the composition according to the invention and optionally with a further layer.
  • this multi-layered product represents a glazing such as architectural glazings, automobile glazing, headlight lenses, spectacle lenses or helmet visors.
  • the invention also relates to a coated substrate comprising a substrate and a coating disposed on or above the substrate, the coating comprising a coating composition according to the present invention.
  • the substrate is a thermoplastic substrate, more preferably a polycarbonate substrate.
  • the invention further relates to a coated substrate comprising a substrate and a coating disposed on or above the substrate, wherein the coating comprises a coating composition according to the invention cured by irradiation with UV light at a dose of at least 2 J / cm 2 .
  • the substrate is a thermoplastic substrate, more preferably a polycarbonate substrate.
  • the invention also relates to a product comprising a coated substrate according to the invention, the article being selected from the group of architectural glazings, automobile glazings, cover plates, helmet visors, housings for electrical appliances, window profiles, body elements and machine covers. Examples
  • PC plates used were GP U099 plates (Bayer MaterialScience GmbH) of size 10 ⁇ 15 ⁇ 0.32 cm. They were rinsed with isopropanol, flashed off, UV pretreated (with a laboratory UV emitter IST-UV Minicure from IST Metz with a UV dose (Hg lamp) of 1.3 J / cm 2 , measured with a dosimeter UV-4C SD of UV-Technik Meyer GmbH as sum of the dose in the wavelength range from 230nm to 445nm). Subsequently, the UV-curable lacquer formulation from a) was applied by flooding. The coated plates were left for 10 min. vented at room temperature, then at 70 ° C for 10 min. dried.
  • UV pretreated with a laboratory UV emitter IST-UV Minicure from IST Metz with a UV dose (Hg lamp) of 1.3 J / cm 2 , measured with a dosimeter UV-4C SD of UV-Technik Meyer GmbH as sum of the dose in the wavelength range from
  • Adhesive tape tear tape 3M Scotch 898 used with cross-hatching (analogous to ISO 2409 or ASTM D 3359), and
  • the initial Haze value of the UV cured first layer coated PC plate was determined according to ASTM D 1003 with a Haze Gard Plus from Byk-Gardner. The coated side of the sample was then scratched using a Taber Abraser Model 5131 from Erichsen according to ISO 52347 or ASTM D 1044 using the CS10F wheels (Type IV, gray color).
  • An AHaze value was determined by determining the final haze value after 1000 revolutions with 500 g application weight.
  • the protective layer should have a sufficiently high scratch resistance. This criterion is achieved in the context of the invention when the Taber value (AHaze after 1000 cycles) is less than or equal to 6.0%. e) Measurement of the resistance to acetone
  • the samples were stored horizontally on a laboratory bench at room temperature (e.g., 23 ° C).
  • a cotton swab soaked in acetone was placed on the sample and covered with a watchglass to prevent evaporation of the solvent. After various exposure times (1 min, 5 min, 15 min, 30 min), the watch glass and the cotton ball were removed.
  • the sample surface was carefully dried with a soft cloth. The surface was visually assessed. In the case of no visible damage the result is noted as plus, in case of visible damage the result is indicated minus.
  • the protective layer should have a sufficiently high resistance to acetone. This criterion is achieved in the sense of the invention if, after 30 minutes, there is no visible damage (corresponding to a designation with plus).
  • the accelerated weathering is carried out according to ASTM G155mod in an Atlas Ci 65 A weathering device.
  • the intensity is 0.75W / (nm * m 2 ) at 340 nm wavelength and a dry / spray cycle is 102: 18 minutes.
  • the black panel temperature is 70 ⁇ 3 ° C and the humidity during the dry cycle is 40 ⁇ 3%.
  • Inner and outer filter are boro filters.
  • the protective layer should have a sufficiently high weathering stability. This criterion is achieved in the context of the invention when the sample is exposed to at least 5000 hours of the above-described weathering without showing turbidity, cracks or delaminations.
  • the pencil hardness was measured in accordance with ISO 15184 or ASTM D 3363.
  • the pencil was drawn at 90 ° angle over an abrasive paper (# 400) to obtain a sharp-edged flat surface.
  • the sample to be measured must lie on a level horizontal surface.
  • the pencil was clamped in a carriage with 0.75 kg (+/- 10 g) support weight, which was placed on the surface to be tested and immediately pushed at least 7 mm above the surface.
  • a damp cloth possibly using isopropanol
  • the markings of the graphite pencil were removed from the surface and these were examined for damage.
  • the hardness of the hardest pencil that did not damage the surface is the so-called pencil hardness:
  • Component A Desmolux ® U680H, a urethane triacrylate containing 20% 1,6-
  • the delivery form of the silica nanoparticles is in methyl ethyl ketone, which is replaced by diacetone alcohol.
  • the solid content of the final dispersion is about 30%.
  • Diameter of the nanoparticles is 10-15nm (measured with light scattering N4 analysis and BET analysis).
  • Component Cl UV absorber Tinuvin ® 479 from Ciba Specialty Chemicals. This compound has the following formula:
  • Component C-2 UV absorber of the following formula:
  • Component C-3 UV-absorber 2- (2'-hydroxy-5'methacryloxyethylphenyl) -2H-benzotriazole available as Tinuvin ® R796 from Ciba Specialty Chemicals. This compound has the following formula:
  • Component C-4 UV Absorber 2- [4 - [(2-Hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6- ⁇ w (2,4-dimethylphenyl) -l, 3,5-triazine, available as Tinuvin ® 405 from Ciba Specialty Chemicals. This compound has the following formula:
  • Component C-5 UV absorber of the general formula Ia with the following groups:
  • T is a urethane acrylate based on HDI (hexamethylene diisocyanate) isocyanurate, which is partially reacted with hydroxyethyl acrylate.
  • HDI hexamethylene diisocyanate
  • Q is -CH 2 -CH 2 - and R is hydrogen.
  • Component C-5 was prepared analogously to the preparation of component C-6.
  • Component C-6 UV absorber of the general formula Ia with the following groups:
  • T is a urethane acrylate based on HDI (hexamethylene diisocyanate) isocyanurate, which is partially reacted with hydroxyethyl acrylate.
  • Q is -CH 2 -CH 2 - and R is hydrogen.
  • the solution was filtered through a layer (10 cm thick) of silica gel. The filtrate was evaporated. The solid was suspended in methanol, placed on the filter and then dried in vacuo at 40 ° C. The intermediate has a melting point of 173 ° C.
  • NCO content of the product ⁇ 0, 1; Content of tin: ⁇ 1 mg / kg
  • Component D HALS system bis (1,2,2,6,6-pentamemyl-4-piperidmyl) - [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate hydroxyphenyl] methyl ] malonate available as Tinuvin ® 144 from Ciba Specialty Chemicals
  • Component E Leveling Agent BYK 300 from BYK Chemie
  • Component F diacetone alcohol component G:
  • Eq component 1-hydroxy-cyclohexyl-phenyl ketone available as Irgacure ® 184 from Ciba Specialty Chemicals component G-2: Ethyl - 2,4,6 - trimethylbenzoylphenylphosphinate available as Lucirin ® TPO-L from BASF AG.
  • Component C as component C, the above-described compound C-6 was used.
  • Component C Tinuvin ® 479 from Ciba Specialty Chemicals
  • Component C Tinuvin ® R796 from Ciba Specialty Chemicals
  • Component C Tinuvin ® 405 from Ciba Specialty Chemicals
  • the coating compositions have good chemical resistance.
  • the change in yellowness index ( ⁇ ) as a function of the weathering time was measured at a layer thickness of 8 ⁇ .
  • the comparative examples show a stronger yellowing and partly a deposit formation during the weathering, as well as a clearly earlier failure of the lacquer layer (occurrence of delaminations and cracking).
  • Comparative Example CEl shows turbid spots on the surface after 2,000 hours of weathering, which continue to occur during weathering. Comparative examples CE2 and CE3 fail (ie delamination or cracking occurs) after 4000 hours of weathering. The Yellowness Index is also rising sharply and is at 4 years in unacceptable levels over 4 in AYL
  • the examples according to the invention show a better migration behavior.
  • CEl as defined above
  • CE4 Composition as described in Table F (comparable to Production Example 1 in WO 2011/040541).
  • Pencil hardnesses were measured for different compositions and different layer thicknesses. As can be seen in Table G, a UV dose below 2 J / cm 2 is not sufficient to completely cure the composition. The surface hardness, as measured with the pencil hardness, is very soft. From a minimum dose of 2 J / cm 2 , the formulation is completely cured and reaches pencil hardnesses of at least H. Only with the formulation according to the invention can such good pencil hardnesses of H be achieved.

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Abstract

L'invention concerne une composition de revêtement comprenant : a) un ou plusieurs précurseurs de polymères, aliphatiques, sélectionnés parmi les composants A.I et éventuellement A.2 : A.I) des oligomères aliphatiques contenant des liaisons uréthane ou ester et présentant au moins deux fonctions acrylate par molécules ou des mélanges d'oligomères correspondants et A.2) des diluants réactifs aliphatiques présentant au moins deux groupes acrylate par molécule ou des mélanges de diluants réactifs correspondants, b) éventuellement un ou plusieurs composés inorganiques à fines particules, c) un absorbeur UV organique d) éventuellement un capteur de radicaux libres de la catégorie des photostabilisants amines à encombrement stérique (HALS = hindered amine light stabilizers), e) éventuellement un ou plusieurs agents mouillants et dispersants, f) éventuellement un ou plusieurs solvants, ainsi que g) un photoamorceur. L'invention concerne par ailleurs un procédé de revêtement d'un substrat, les substrats munis de revêtements et ainsi obtenus, de même que l'utilisation desdits substrats munis de revêtements. Les absorbeurs UV C) sont des absorbeurs de formule (Ia) et (Ib), B-X-O-C(=O)-C(R)=CH2 (Ib), formule dans laquelle B désigne (I).
EP14704099.2A 2013-02-01 2014-01-30 Composition de revêtement séchant par rayonnement ultraviolet Withdrawn EP2951251A1 (fr)

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JP6354665B2 (ja) * 2014-06-23 2018-07-11 信越化学工業株式会社 光硬化性コーティング組成物及び被覆物品
KR101746460B1 (ko) 2015-11-20 2017-06-13 현대자동차주식회사 폴리카보네이트 글레이징용 코팅도료 조성물로 코팅된 도장품
BR112018067643A2 (pt) * 2016-03-04 2019-01-02 Dow Global Technologies Llc composição de acrilato de uretano curável
EP3615622A4 (fr) * 2017-04-25 2020-12-16 Basf Se Compositions de revêtement ayant des absorbeurs d'ultraviolets liés par covalence
KR102193014B1 (ko) * 2017-10-11 2020-12-18 주식회사 엘지화학 항균성 고분자 코팅 조성물 및 항균성 고분자 필름
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