WO2019241679A1 - Revêtements transparents bloquant les uv pouvant être durcis par des uv - Google Patents

Revêtements transparents bloquant les uv pouvant être durcis par des uv Download PDF

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WO2019241679A1
WO2019241679A1 PCT/US2019/037262 US2019037262W WO2019241679A1 WO 2019241679 A1 WO2019241679 A1 WO 2019241679A1 US 2019037262 W US2019037262 W US 2019037262W WO 2019241679 A1 WO2019241679 A1 WO 2019241679A1
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photo
composition
weight
coating composition
concentration
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PCT/US2019/037262
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Puruswottam Aryal
Glenn Allen MESA, Jr.
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Metashield, Llc
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    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

Definitions

  • the present invention relates to coatings that are UV curable and UV blocking/absorbing and to photo-initiator combinations for use in such coatings.
  • UV curable coating that blocks UV up to 380 nm or 400 nm because the UV blocking properties of the coating itself prevent the complete curing of UV curing through the full thickness of the coating. This challenge increases when the coating needs to be optically clear with a very low yellowness index to be acceptable.
  • photo- initiators are available that absorb and block UV light in the visible wavelength range, such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) and phenyl-bis(2,4,6- trimethylbenzoyl)phosphine oxide (BAPO), these photo-initiators yellow unacceptably upon UV exposure.
  • Coatings with these photo-initiators bleach upon exposure to light and heat for a few hours after UV curing, but still look too yellow to be acceptable when a color neutral optically transparent coating is desired. Accordingly, improved photo-initiators and photo-initiator combinations are desirable to improve curing while minimizing yellowness in certain higher wavelengths above about 380 nm.
  • the present invention relates to UV resistant UV curable acrylate coating compositions having a photo-initiator combination comprising:
  • the acrylate coating after curing upon exposure to UV light emitted from a UV H bulb having a mercury spectral output has a thickness of from about 20 to about 32 pm and a Delta Yellowness Index less than or equal to about 5.3.
  • the UV resistant UV curable acrylate coating composition, the first photo- initiator compound has a concentration of from about 2% to about 8% by weight of the total coating composition.
  • the first photo-initiator compound has a concentration of from about 3.85% to about 7.96% by weight of the total coating composition. In one exemplary embodiment, the first photo-initiator compound has a concentration of about 3.85% by weight of the total coating composition.
  • the first photo-initiator compound has a concentration of about 7.96% by weight of the total coating composition.
  • the second photo-initiator compound has a concentration of from about 0.2% to about 2% by weight of the total coating composition.
  • the second photo-initiator compound has a concentration of from about 0.2% to about 1.0% by weight of the total coating composition.
  • the second photo-initiator compound has a concentration of from about 0.22% to about 0.42% by weight of the total coating composition.
  • the second photo-initiator compound has a concentration of about 0.42% by weight of the total coating composition.
  • the second photo-initiator compound has a concentration of about 0.22% by weight of the total coating composition.
  • the first photo-initiator is an acetophenone has a concentration of from about 3.85% to about 7.96%
  • the second photo-initiator compound has a concentration of from about 0.22% to about 0.42% by weight of the total coating composition.
  • the first photo-initiator is 2,2- di ethoxy acetophenone and the second photo-initiator compound is diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO).
  • TPO diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide
  • the first photo-initiator compound is selected from one or more of 4'- ethoxyacetophenone, 4'-hydroxyacetophenone, 2,5-dimethylbenzophenone, 4- hydroxybenzophenone, and 1 -hydroxy cyclohexyl phenyl ketone, or combinations thereof.
  • the first photo-initiator compound is 2,2-diethoxyacetophenone.
  • the second photo-initiator compound is selected from one or more of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and bis(2,4,6-trimethylbenzoyl)- phenylphosphineoxide, or combinations thereof.
  • the second photo-initiator compound is diphenyl(2,4,6- trimethylbenzoyl)phosphine oxide.
  • the first photo-initiator compound is 2,2- diethoxyacetophenone and the second photo-initiator compound is diphenyl(2,4,6- trimethylbenzoyl)phosphine oxide.
  • the concentration of the first photo-initiator compound 2,2- diethoxyacetophenone is about 3.85% by weight of the total coating composition and the concentration of the second photo-initiator compound diphenyl(2,4,6- trimethylbenzoyl)phosphine oxide is 0.22% by weight of the total coating composition.
  • the Delta Yellowness Index of the cured coating composition is less than about 3.
  • the Delta Yellowness Index of the cured coating composition ranges from about 1 to about 3.
  • the Delta Yellowness Index of the cured coating composition is about 1.
  • the thickness of the cured coating composition is from about 15 pm to about 30 pm.
  • the thickness of the cured coating composition is about 20 pm.
  • Fig. 1 is a graph showing transmission spectra of the coatings MS7UV380 (dashed line) and MS7UV400 (solid line).
  • Fig. 2 is a graph showing Tinuvin 384-2 % as a function of total weight.
  • the UV photopolymerizable compositions may include free radically polymerizable monomers, oligomers, and polymers having one or more ethyl enically unsaturated acrylic groups. Suitable compounds contain at least one ethylenically unsaturated bond and are capable of undergoing addition polymerization. Examples of useful ethylenically unsaturated acrylate compounds include acrylic acid esters, methacrylic acid esters, hydroxy-functional acrylic acid esters, hydroxy-functional methacrylic acid esters, and combinations thereof.
  • acrylate and acrylic refer to the same chemical functionality.
  • (meth)acrylate refers to both the acrylate (without the methyl group at the position of the ethylene function) and methacrylate (with the methyl group at the position of the ethylene function) variants of the monomer
  • the UV curable compositions may also contain monomers having hydroxyl groups and ethylenically unsaturated groups in a single molecule.
  • examples of such materials include hydroxyalkyl (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; glycerol mono- or di-(meth)acrylate; trimethylolpropane mono- or di- (meth)acrylate; pentaerythritol mono-, di-, and tri-(meth)acrylate; sorbitol mono-, di-, tri-, tetra-, or penta-(meth)acrylate; and 2,2-bis[4-(2-hydroxy-3-ethacryloxypropoxy)phenyl]propane (bisGMA).
  • Suitable ethylenically unsaturated compounds are available from a wide variety of commercial sources, such as Sigma-Aldrich, St. Louis.
  • the (meth)acrylates described and claimed herein are multifunctional, meaning that they can be difunctional, trifunctional, tetrafunctional, pentafunctional, hexafunctional or higher functional, or combinations thereof. Typically, the higher the functionality, the greater is the crosslink density. (Meth)acrylates have slower curing than the acrylates.
  • the two, three, four, five or six or more (meth)acrylic functional groups may be selected from one or more of, for example, pentaerythritol triacrylate, pentaerythritol tetraacrylate,
  • Free radically polymerizable compounds include di- or poly-(meth)acrylates (i.e., acrylates and methacrylates) such as glycerol tri(meth)acrylate, ethyleneglycol di(meth)acrylate,
  • diethyleneglycol di(meth)acrylate triethyleneglycol di(meth)acrylate, 1, 3-propanediol di(meth)acrylate, trimethyl olpropane tri(meth)acrylate, l,2,4-butanetriol tri(meth)acrylate, 1,4- cyclohexanediol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, sorbitol hex(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, bis[l-(2-acryloxy)]-p-ethoxyphenyldimethylmethane, bis[l- (3-acryloxy-2-hydroxy)]p-propoxyphenyldimethylmethane, ethoxylated bisphenol A
  • (meth)acrylamides i.e., acrylamides and methacrylamides
  • urethane (meth)acrylates the bis-(meth)acrylates of
  • polyethylene glycols preferably of molecular weight 200-500
  • vinyl compounds such as styrene, diallyl phthalate, divinyl succinate, divinyl adipate and divinyl phthalate.
  • suitable free radically polymerizable compounds include siloxane-functional (meth)acrylates. Mixtures of two or more free radically polymerizable compounds can be used if desired.
  • the coating compositions comprise one or more photocurable acrylate or methacrylate monomers or copolymers, which react to form a polymeric matrix having high surface hardness and high crosslinking density of coatings.
  • the curable acrylate may comprise a first multifunctional acrylate monomer or oligomer with three or more functional polymer bonding groups.
  • the curable acrylate may also comprise aliphatic urethane acrylates.
  • the acrylate polymer may be obtained using multifunctional acrylate monomers such as trimethylolpropane triacrylate (TMPTA) and dipentaerythritol penta-hexa acrylate.
  • TMPTA trimethylolpropane triacrylate
  • dipentaerythritol penta-hexa acrylate dipentaerythritol penta-hexa acrylate.
  • Multifunctional aliphatic urethane acrylates include, for example, EBECRYL® 1290 (a hexafunctional aliphatic urethane acrylate oligomer) and EBECRYL® 225 (an aliphatic urethane -deca-acrylate monomer), commercially available from Allnex (Luxembourg, Belgium).
  • the multifunctional acrylate may be preloaded with nanoparticles.
  • nanoparticles may be metal oxide nanoparticles, such as silica nanoparticles.
  • TMPTA which is commercially available as NANOCRYL ®
  • the acrylate monomer may be present in a concentration range of from about 10% to about 50%.
  • the acrylate monomer may be present in a concentration range of from about 10% to about 46%.
  • the acrylate monomer may be present in a concentration range of from about 35% to about 50%.
  • the acrylate monomer may also be present in a concentration range of about 40% to about 41% by weight of the total composition.
  • the acrylate portion of the composition may also include two or more of the acrylate monomer compounds described above.
  • the acrylate portion of the composition may also include a second multifunctional acrylate monomer or oligomer having two or more functional polymer bonding groups.
  • the second acrylate monomer or copolymer may include any of the multifunctional acrylate monomers or oligomers described above for the first acrylate monomer or oligomer that have two or more functional polymer bonding groups.
  • the second acrylate monomer may be dipentaerythritol penta-hexa acrylate.
  • the second acrylate monomer or oligomer having two or more functional polymer bonding groups may be present in a concentration of from about 5% to about 40% by weight of the total composition.
  • the second acrylate monomer having two or more functional polymer bonding groups may be present in a concentration range of from about 5% to about 15% by weight of the total composition.
  • the second acrylate monomer having two or more functional polymer bonding groups may be present in a concentration range of from about 7% to about 38% by weight of the total composition.
  • the second acrylate monomer having two or more functional polymer bonding groups may be present in a concentration range of from about 7% to about 12% by weight of the total composition.
  • the second multifunctional acrylate monomer may be present in a concentration of about 8% by weight of the total composition.
  • the curable acrylate compound may include a third polyfunctional acrylate monomer or oligomer having one or more bonding functional groups.
  • Such acrylate monomers or oligomers may be, for example, l,6-hexanediol diacrylate.
  • the multifunctional acrylate may be present in a concentration of from about 5% to about 30% by weight of the total composition.
  • the third multifunctional acrylate may be present in a concentration range of from about 6% to about 20% by weight of the total composition.
  • the third multifunctional acrylate may be present in a concentration range of from about 9% to about 12% by weight of the total composition.
  • the third acrylate may be present in a concentration of about 12% by weight of the total composition.
  • the acrylate monomers described above may also be combined with a plurality of free-radical photo-initiators to initiate polymerization of the acrylate monomers.
  • the UV resistant UV curable acrylate monomers or copolymers are curable using first photo- initiator that is primarily photoactivated by UA-B and UV-C light.
  • Suitable phenyl ketone-based photo-initiators may include one or more phenyl ketone, such as acetophenone and/or benzophenone, and/or other phenyl ketone-based compound.
  • the phenyl ketone photo-initiator compound may be just one of an acetophenone, benzophenone, and/or other phenyl ketone-based compound or a mixture of two or more of these compounds.
  • the UV resistant UV curable acrylate monomers or copolymers are curable using a second photo-initiator that is primarily photoactivated by UV-A light.
  • photo-initiators may include compounds having a reactive phosphoryl group having a phosphorous-oxygen double bond.
  • Suitable compounds having a reactive phosphoryl group include phosphine oxides, which are phosphorus compounds having the formula OPX3, where X may be an organic alkyl or aryl group or an inorganic group, such as a halogen group.
  • Such phosphine oxide compounds may be used alone or in a mixture of two or more of these compounds.
  • a photo-initiator is typically added to the mixture of polymerizable ingredients.
  • the photo- initiator is sufficiently miscible with the resin system to permit ready dissolution in (and discourage separation from) the polymerizable composition.
  • the photo-initiator is present in the composition in effective amounts, such as from about 0.1% weight percent to about 5.0% by weight percent of the total weight of the composition.
  • the mixture of monomers is photopolymerizable and the composition contains a photo-initiator (i.e., a photo-initiator system) that upon irradiation with actinic radiation initiates the photo-initiator (i.e., a photo-initiator system) that upon irradiation with actinic radiation initiates the photo-initiator (i.e., a photo-initiator system) that upon irradiation with actinic radiation initiates the
  • the photo-initiator system typically has a functional wavelength range from about 200 nm to about 400 nm.
  • the photo-initiator system may also have a functional wavelength range from about 200 nm to about 410 nm.
  • the photo-initiator system may also have a functional wavelength range from about 200 nm to about 420 nm.
  • Suitable photo-initiators for polymerizing free radically photopolymerizable compositions include binary and tertiary systems.
  • Typical tertiary photo-initiators include an iodonium salt, a photosensitizer, and an electron donor compound as described in U.S. Pat. No. 5,545,676 (Palazzotto et ah).
  • Iodonium salts include diaryl iodonium salts, e.g., diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, and diphenyliodonium tetrafluoroboarate.
  • Some photosensitizers may include monoketones and diketones (e.g. alpha diketones) that absorb some light within a range of about 300 nm to about 800 nm (or about 400 nm to about 500 nm) such as camphorquinone, benzil, furil, 3,3,6,6-tetramethylcyclohexanedione, phenanthraquinone and other cyclic alpha diketones. Of these camphorquinone is typical.
  • Electron donor compounds include substituted amines, e.g., ethyl 4-(N,N-dimethylamino)benzoate.
  • Acetophenone and acetophenone derivative photo-initiators can include a-hydroxy-cycloalkyl phenyl ketones or a-hydroxyalkyl phenyl ketones. Particular examples include acetophenone, p- tert-butyl trichloroacetophenone, chloroacetophenone, 2,2-diethoxy acetophenone, hydroxy acetophenone, 2,2-dimethoxy-2'-phenyl acetophenone, 2-aminoacetophenone, and dialkyl aminoacetophenone, 2-hydroxy-2-methyl propiophenone, 2-hydroxy-4'-(2- hydroxyethoxy)-2- methyl propiophenone, 2-hydroxy-2,2-dimethylacetophenone, acetonaphthoquinone, valerophenone, hexanophenone, a-phenylbutyrophenone, dibenzosuberone, p-diacetylbenzene, 4'-methoxy
  • 3-dioxolanes benzoin alkyl ethers and benzil ketals, e.g. dimethyl benzil ketal, phenylglyoxalic esters and derivatives thereof, e.g. methyl a-oxo benzeneacetate, oxo-phenyl-acetic acid 2-(2- hydroxy-ethoxy)-ethyl ester, dimeric phenylglyoxalic esters, e.g. 9H-thioxanthene-2- carboxaldehyde 9-oxo-2-(0-acetyloxime), per- esters, e,g. benzophenone tetracarboxylic peresters as described for example in EP 126541.
  • Free radical acetophenone photo-initiators are available commercially as (l-[4-(2- hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-l-propan-l-one) (IRGACURE ® 2959 from CIBA), 2,2-di-sec-butoxyacetophenone, 2,2-diethoxy-2-phenyl-acetophenone, 1 -hydroxy- cyclohexyl -phenyl-ketone (IRGACURE ® 184 from CIBA) and 2-hydroxy-2-methyl-l- phenylpropan-l-one (such as DAROCUR® 1173 sold by CIBA); alpha amino ketones, particularly those containing a benzoyl moiety, otherwise called alpha-amino acetophenones, such as 2-hydroxy-l- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl ⁇ - 2-methyl-propan-
  • ESACURE KIP 1001 M® oxime- esters, such as l,2-octanedione l-[4-(phenylthio)phenyl]-2-(0-benzoyl oxime) (IRGACURE® OXEOl ), and ethanone l-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-l-(0-acetyloxime) (IRGACURE® OXE02).
  • oxime- esters such as l,2-octanedione l-[4-(phenylthio)phenyl]-2-(0-benzoyl oxime) (IRGACURE® OXEOl )
  • ethanone l-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-l-(0-acetyloxime) IRGACURE® OXE02
  • Benzophenones and related aromatic ketones may include, for example, benzophenone, benzophenone derivatives, such as xanthones, thioxanthones such as 2-chlorothioxanthone, 2- methylthioxanthone, 2-isopropylthioxanthone, camphor quinone, methyl benzophenones, such as
  • Photo-initiators based on acyl phosphine oxides are photosensitive at longer wavelengths (UV-A or visible light).
  • UV-A or visible light The UV photo-initiators used for polymerizing free radically
  • photopolymerizable compositions may include the class of phosphine oxides that typically initiate polymerization at a functional wavelength range of about 380 nm to about 1200 nm.
  • Some phosphine oxide free radical initiators such as acyl and bisacyl phosphine oxides, initiate polymerization at a functional wavelength range of about 380 nm to about 450 nm.
  • acylphosphine oxide compounds are monoacyl and bisacyl phosphine oxides and sulphides; monoacyl phosphine oxides, e.g. (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, ethyl (2,4,6 trimethylbenzoyl phenyl) phosphinic acid ester; bisacyl-phosphine oxides, e.g.
  • oxidestriacyl phosphine oxides methyl isobutyryl-methylphosphinate, methyl isobutyryl- phenylphosphinate, methyl pivaloylphenylphosphinate, methyl 2-ethylhexanoyl- phenyl phosphinate, isopropyl pivaloyl -phenyl phosphinate, methyl p-toluyl phenyl phosphinate, methyl o-toluyl-phenylphosphinate, methyl 2,4-dimethylbenzoyl-phenylphosphinate, isopropyl p-tert-butyl-phenylphosphinate, methyl pivaloyl-(4-methylphenyl)phosphinate, vinyl pivaloyl- phenylphosphinate, methyl acryloyl-phenylphosphinate, isobutyryl-diphenylphosphine oxide
  • trimethylbenzoylethoxydiphenyl phosphine oxide bisacylphosphine oxides (BAPO) or bis(2,6- dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; benzyltrimethylbenzoyl diphenyl phosphinoxide; and mixtures thereof.
  • Acyl phosphine oxide photo-initiators are available commercially as bis(2,4,6- trimethylbenzoyl)phenyl phosphine oxide (IRGACURE® 819, Ciba Specialty Chemicals, Tarrytown, N.Y.), bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) phosphine oxide (CGI® 403, Ciba Specialty Chemicals), a 25:75 mixture, by weight, of bis(2,6-dimethoxybenzoyl)- 2,4,4-trimethylpentyl phosphine oxide and 2-hydroxy-2-methyl-l-phenylpropan-l-one
  • Phosphine oxide photo- initiators may include acyl phosphine oxide photo-initiators, for example, diphenyl(2,4,6- trimethylbenzoyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide;
  • IRGACURE® 1800 (manufactured by Ciba Specialty Chemicals Corporation) which is a 75%/25% mixture of 1 -hydroxy cyclohexyl phenyl ketone (IRGACURE 184®, Ciba Specialty Chemicals Corporation) and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide (Ciba Specialty Chemicals Corporation); IRGACURE® 1850 (Ciba Specialty Chemicals Corporation) which is a 50%/50% mixture of the preceding compounds; bis(2,4,6- trimethylbenzoyl)phenyl phosphine oxide (IRGACURE® 819, Ciba Specialty Chemicals Corporation); 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (LUCIRIN® TPO, BASF AG); DAROCUR® 4265 which is a 50%/50% mixture of 2-hydroxy-2-methyl-l-phenylpropane-l-
  • photo-initiators may be 2,2-diethoxyacetophenone, diphenyl(2,4,6- trimethylbenzoyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, dimethoxyphenyl acetophenone, and 2,5-dimethylbenzophenone
  • photo-initiators is 2,2-diethoxyacetophenone, diphenyl(2,4,6- trimethylbenzoyl)phosphine oxide.
  • photo-initiators is 2,2-diethoxyacetophenone and bis(2,4,6- trimethylbenzoyl)-phenylphosphineoxide.
  • photo-initiators is dimethoxyphenyl acetophenone and diphenyl (2,4, 6-trimethylb enzoyl)phosphine oxi de .
  • photo-initiators is 2,5-dimethylbenzophenone and
  • photo-initiators is 2,5-dimethylbenzophenone and bis(2,4,6- trimethylbenzoyl)-phenylphosphineoxide.
  • the acetophenones, benzophenones, and related phenyl ketones (or total combination of these compounds) may be present in a concentration of from about 2% to about 10% by weight of the total coating composition.
  • the acetophenones, benzophenones, and related phenyl ketones (or total combination of these compounds) may be present in a concentration of about 3.88% by weight of the total coating composition.
  • the acyl phosphine oxide photo-initiator may be present in a
  • the acyl phosphine oxide photo-initiator may also be present in a concentration range of from about 0.11% to about 0.42% by weight of the total coating composition.
  • the acyl phosphine oxide photo-initiator may also be present in a concentration of about 0.22 % by weight of the total coating composition.
  • the coating compositions may also include one or more UV blocking/absorbing compound, such as a tetratriazole type UV blocker.
  • tetratriazole UV blockers include, for example, hydroxyphenyl-triazine or hydroxyphenylbenzotriazole class UV blocking compounds, which are commercially available as TINUVIN ® 400, TINUVIN ® 384-2, and TINUVIN ® 328 (BASF Corporation).
  • the UV blocking compound may be TINUVIN® 384-2, which can be present in a concentration ranging from about 1% to about 15% by weight of the total composition. In other embodiments, the UV blocking compound may be TINUVIN 384-2 present in a concentration ranging from about 1.5 to about 2.4 grams. In some particular embodiments, the TINUVIN® 384-2 compound may be present in a concentration of about 9.93% by weight. However, TINUVIN® 384-2 does not block completely up to 400 nm. Thus, in some embodiments, the UV blocking/absorbing compound may be mixed with a second UV blocking/absorbing compound that blocks UV up to 400 nm, such as TINUVIN® 400.
  • the concentration of the UV blocking/absorbing compound depends on the wavelengths that need to be completely blocked and the thickness of the coating, which is a function of the particular application of the coating.
  • the concentration of the UV blocking/absorbing compound may be from about 1% to about 15% by weight of the total composition.
  • the concentration of the UV blocking/absorbing compound may be from about 6% to about 15% by weight of the total composition.
  • the concentration of the UV blocking/ab sorbing compound may be about 10% by weight of the total composition.
  • the coating composition may also include an optical brightener.
  • Optical brighteners generally decrease the yellowness of the coating.
  • Optical brighteners such as UVITEX ® OB (2,5-Bis(5- tert-butyl-2-benzoxazolyl)thiophene), MPI ® BRIGHT FP 127 (4,4'-bis(2-methoxystyryl)-l,T- biphenyl), MPI BRIGHT ® ER-3 (4,4'-(p-phenylenediethene-2,l-diyl)bisbenzonitrile).
  • UVITEX OB is available commercially from BASF Corporation.
  • MPI BRIGHT ® is available
  • the optical brightener may be 2,5- Bis(5-tert-butyl-2-benzoxazolyl)thiophene).
  • the concentration of the optical brightener may depend on the wavelengths that need to completely blocked and the thickness of the coating.
  • the concentration of the optical brightener may be from about greater than 0% to about 1.5% by weight of the total coating composition.
  • the solvents used in the compositions disclosed herein may be organic solvents, such as acetone, ethanol, isopropyl alcohol, dichloromethane, toluene, benzene, hexane, n-butyl acetate, 1- methoxy-2-proponol (such as Dowanol PM glycol ether), propylene glycol monomethyl ether acetate (PGMEA),etc. or a combination of two or more of these solvents.
  • organic solvents such as acetone, ethanol, isopropyl alcohol, dichloromethane, toluene, benzene, hexane, n-butyl acetate, 1- methoxy-2-proponol (such as Dowanol PM glycol ether), propylene glycol monomethyl ether acetate (PGMEA),etc. or a combination of two or more of these solvents.
  • the solvent may be in a concentration of from about greater than 0 to about 50% by weight of the total coating composition.
  • composition may further comprise a solvent having a Hildebrand solubility parameter d value of less than about 7.2 cal 1/2 cm 3/2 and a hydrogen bonding index of less than about 13.6 kJ/mol.
  • compositions disclosed herein may include a flow additive for wetting the substrate and promoting even flow of the coating over the substrate.
  • the substrate wetting or flow additive may be a silicone or polyacrylate based wetting, flowing and leveling additive, such as TEGO ® Rad 2100, BYK ® 306, BYK ® 361 N, BYK ® 378, TEGO ® Twin 4000, TEGO ® Twin 4100, TEGO ® Twin 4200, TEGO ® Flow 300, TEGO ® Flow 460 N, TEGO ® Flow ATF 2, and similar wetting, flowing and leveling additives.
  • the substrate wetting and flow additive may be in a concentration of greater than about 0% to about 3% by weight of the total coating composition
  • the coating compositions of the present invention may also include a blue dye for the purposes of diminishing the yellowness of the coating.
  • a suitable blue dye may be l-[(4- methylphenyl)amino]-4-hydroxy-9,l0-anthracenedione.
  • the blue day may be present in a concentration of greater than about 0% to about 3% by weight of the total coating composition.
  • compositions MS7ETV380 and MS7ETV400 were made as described below by mixing the ingredients (in any order) and stirring for 2 hours.
  • NANOCRYL C 150 is trimethylpropane triacrylate with 50% silica by weight.
  • Dipentaerythritol penta-hexa acrylate is an acrylate used to improve the hardness of the
  • l,6-Hexanediol diacrylate is a difunctional acrylate used to lower the viscosity of the solution for spraying
  • 2,2-Diethoxyacetophenone is a free radical photo-initiator that has high absorption
  • this photo-initiator provides good surface cure, but not depth cure due to low penetration depth
  • Diphenyl (2, 4, 6-trimethylbenzoyl)phosphine oxide is a free radical photo-initiator used for good depth of cure
  • TINUVIN 384-2 is a UV blocking compound (alternatives such as TINUVIN 400 can be used too)
  • 2,5-Bis(5-tert-butyl-2-benzoxazolyl)thiophene is an optical brightener. Its function is to absorb UV and reemit blue light
  • TEGO Rad 2100 and TEGO Flow 460 N are used as surface wetting and flow additives
  • the MS7UV380 and MS7UV400 coatings can be cured with an H type UV bulb, having a mercury spectral output, which is a surprising result.
  • DPTBP diphenyl (2,4,6- trimethylbenzoyl)phosphine oxide
  • surface cure occurs with the H bulb which leads to the formation of a skin on top of liquid coating underneath.
  • diphenyl (2,4,6- trimethylbenzoyl)phosphine oxide one would expect that the coating would cure better with either a D type UV bulb or a V type UV bulb due to a greater penetration depth into the coating.
  • the coating does not cure with a D or V bulb, unless the amount of diphenyl (2,4,6- trimethylbenzoyl)phosphine oxide is increased significantly, which leads to unacceptable yellowing of the coating.
  • the coating cures well with the combination of an acetophenone photo-initiator at a concentration ranging from about 2% to about 10%, in combination with an acylphosphine oxide photo-initiator at a concentration ranging from about 0.1 to about 2%, with an H bulb.
  • the concentration of the acetophenone photo-initiator may be about 3.88%.
  • the concentration of the acylphosphine oxide photo-initiator may be about 0.22%.
  • MS7UV380 and MS7UV400 block up to about 380 nm and about 400 nm, respectively. Due to a sharp absorption onset of the coatings, and hence minimum light absorption above 400 nm, the coatings are almost color neutral.
  • the graph shown in FIG. 2 shows various percentages of liquid UV absorber of the
  • hydroxyphenylbenzotriazole class were used starting at 8.90% and up to 14.66%. All were low haze, low Yellowness index, and high transmission about 90%). Multiple runs were averaged. So each line represents an average of multiple samples with the same percentage and approximately the same thickness. All testing was done with a UV-VIS on transmission mode and a crossover of 420nm. Table A - Examples of Coatings
  • the Delta Yellowness Index was evaluated using the D65 source spectrum with 2° observer and CIE 1931 color matching functions to calculate the xyz color coordinates from the transmittance data obtained from a spectrophotometer. ASTM E313 was then used to calculate the Delta Yellowness Index from the color coordinates.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne des revêtements qui peuvent être durcis par des UV et bloquant/absorbant les UV et des associations de photo-initiateurs destinées à être utilisées dans de tels revêtements comprenant un premier composé photo-initiateur photosensible à des longueurs d'onde d'UV-B et d'UV-C comportant un groupe cétone et un second composé photo-initiateur photosensible à des longueurs d'onde d'UV-A ou de la lumière visible sélectionnés parmi des composés d'oxyde d'acylphosphine.
PCT/US2019/037262 2018-06-15 2019-06-14 Revêtements transparents bloquant les uv pouvant être durcis par des uv WO2019241679A1 (fr)

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US62/685,752 2018-06-15
US201862686336P 2018-06-18 2018-06-18
US62/686,336 2018-06-18
US201862718184P 2018-08-13 2018-08-13
US62/718,184 2018-08-13

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Cited By (1)

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CN114163855A (zh) * 2021-12-20 2022-03-11 浙江商林科技股份有限公司 一种uv与湿气双固化三防漆及制备方法

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US20040152798A1 (en) * 2001-04-27 2004-08-05 Peter Weissman Photo-initiator compositions
US20070054234A1 (en) * 2002-06-28 2007-03-08 3M Innovative Properties Company Processes for forming dental materials and device
US20140178692A1 (en) * 2012-12-20 2014-06-26 Momentive Performance Materials Inc. Radiation curable hardcoat with improved weatherability
US9133297B2 (en) * 2003-11-17 2015-09-15 Allnex Ip S.À.R.L. Ultraviolet-curable polyols and polyurethane compositions made therefrom
US20170260417A1 (en) * 2014-09-11 2017-09-14 Sherwin-Williams Deutschland Gmbh Coating composition for wood finishing
US9834634B2 (en) * 2014-02-27 2017-12-05 Akzo Nobel Coatings International, B.V. Acrylic resins and powder coating compositions and powder coated substrates including the same
WO2017221102A1 (fr) * 2016-06-21 2017-12-28 Sabic Global Technologies B.V. Compositions polymères présentant une réflectivité et une conductivité thermique

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Publication number Priority date Publication date Assignee Title
US20040152798A1 (en) * 2001-04-27 2004-08-05 Peter Weissman Photo-initiator compositions
US20070054234A1 (en) * 2002-06-28 2007-03-08 3M Innovative Properties Company Processes for forming dental materials and device
US9133297B2 (en) * 2003-11-17 2015-09-15 Allnex Ip S.À.R.L. Ultraviolet-curable polyols and polyurethane compositions made therefrom
US20140178692A1 (en) * 2012-12-20 2014-06-26 Momentive Performance Materials Inc. Radiation curable hardcoat with improved weatherability
US9834634B2 (en) * 2014-02-27 2017-12-05 Akzo Nobel Coatings International, B.V. Acrylic resins and powder coating compositions and powder coated substrates including the same
US20170260417A1 (en) * 2014-09-11 2017-09-14 Sherwin-Williams Deutschland Gmbh Coating composition for wood finishing
WO2017221102A1 (fr) * 2016-06-21 2017-12-28 Sabic Global Technologies B.V. Compositions polymères présentant une réflectivité et une conductivité thermique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114163855A (zh) * 2021-12-20 2022-03-11 浙江商林科技股份有限公司 一种uv与湿气双固化三防漆及制备方法

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