WO2019000375A1 - Nanoparticules inorganiques à surface modifiée et leur utilisation - Google Patents

Nanoparticules inorganiques à surface modifiée et leur utilisation Download PDF

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Publication number
WO2019000375A1
WO2019000375A1 PCT/CN2017/091051 CN2017091051W WO2019000375A1 WO 2019000375 A1 WO2019000375 A1 WO 2019000375A1 CN 2017091051 W CN2017091051 W CN 2017091051W WO 2019000375 A1 WO2019000375 A1 WO 2019000375A1
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Prior art keywords
group
optionally substituted
surface modified
inorganic nanoparticles
meth
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PCT/CN2017/091051
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English (en)
Inventor
Puwei Liu
Nicolas BALL-JONES
Chunhua GU
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Henkel Ag & Co. Kgaa
Henkel IP & Holding GmbH
Henkel (China) Co., Ltd.
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Application filed by Henkel Ag & Co. Kgaa, Henkel IP & Holding GmbH, Henkel (China) Co., Ltd. filed Critical Henkel Ag & Co. Kgaa
Priority to PCT/CN2017/091051 priority Critical patent/WO2019000375A1/fr
Priority to TW107120271A priority patent/TW201905058A/zh
Publication of WO2019000375A1 publication Critical patent/WO2019000375A1/fr

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    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals

Definitions

  • the present invention relates to surface modified inorganic nanoparticles and use thereof.
  • the invention relates tosurface modified inorganic nanoparticles having a high refractive index of at least 1.50, and their use as fillers in adhesives, sealants and/or potting materials, especially in optical clear adhesives (OCAs) , such as liquid optical clear adhesives (LOCAs) .
  • OCAs optical clear adhesives
  • LOCAs liquid optical clear adhesives
  • US 8535576 B2 discloses a pressure-sensitive adhesive comprising a biphenyl monomer which has a high refractive index.
  • the adhesives have a refractive index of at least 1.54, and sufficient conformability, tack and adhesion to form a bond to a substrate at room temperature.
  • the present invention provides surface modified inorganic nanoparticles, which can be used as fillers in OCAs (such as LOCAs) , wherein inorganic nanoparticles are surface modified with a surface modifier (also referred to as a “surface treating agent” or a “ (surface) modifier” ) comprising an organic compound.
  • a surface modifier also referred to as a “surface treating agent” or a “ (surface) modifier”
  • the organic compound has an intrinsic high refractive index value (RI) of at least 1.50.
  • the organic compound used in this invention normally contains a functional group capable of forming covalent bond or ligand with the surfaces of the inorganic nanoparticles.
  • the organic compound has at least one group selected from hydroxyl group, carboxyl group, anhydride groups, isocyanate group and hydrolysable silane groups; and has at least one optionally substituted aryl or arylene moiety.
  • the present invention also provides a curable adhesive composition comprising surface modified inorganic particles according to the present invention and a curable resin component, and a cured product of the curable adhesive composition.
  • the present invention also provides use of the surface modified inorganic particles according to the present invention as fillers in adhesives, sealants and/or potting materials.
  • (meth) acrylate means acrylate and/or methacrylate.
  • refractive index is defined herein as the absolute refractive index of a material (e.g., inorganic nanoparticle orcurable adhesive composition) which is understood to be the ratio of the speed of light in vacuum to the speed of the light in that material, with the light being sodium yellow light at a wavelength of about 583.9 nanometers (nm) .
  • the refractive index can be measured using known methods and is generally measured using an Abbe Refractometer.
  • alkyl used alone or as part of a larger moiety, refers to an optionally substituted straight or branched chain hydrocarbon group having 1-12, 1-10, 1-8, 1-6, 1-5, 1-4, 1-3, or 1-2 carbon atoms.
  • alkenyl used alone or as part of a larger moiety, refers to an optionally substituted straight or branched chain hydrocarbon group having at least one double bond and having 2-12, 2-10, 2-8, 2-6, 2-5, 2-4, or 2-3 carbon atoms.
  • alkynyl used alone or as part of a larger moiety, refers to an optionally substituted straight or branched chain hydrocarbon group having at least one triple bond and having 2-12, 2-10, 2-8, 2-6, 2-5, 2-4, or 2-3 carbon atoms.
  • alkoxy refers to an alkyl group, as previously defined, attached to the principal carbon chain through an oxygen ( “alkoxy” ) atom.
  • aryl used alone or as part of a larger moiety, e.g., "aralkyl”, refer to an optionally substituted aromatic hydrocarbon moiety comprising one to three aromatic rings.
  • Aryl groups include, without limitation, optionally substituted phenyl, naphthyl, or anthracenyl.
  • aryl as used herein, also include groups in which an aryl ring is fused to one or more cycloaliphatic rings to form an optionally substituted cyclic structure such as a tetrahydronaphthyl, indenyl, or indanyl ring.
  • aralkyl refers to an aryl group covalently attached to an alkyl group, either of which independently is optionally substituted.
  • the aralkyl group is C 6-10 aryl-C 1-6 alkyl, including, without limitation, benzyl, phenethyl, and naphthylmethyl.
  • alkaryl refers to an alkyl group covalently attached to an aryl group, either of which independently is optionally substituted.
  • the alkaryl group is C 1-6 alkyl-C 6-10 aryl.
  • heteroaryl used alone or as part of a larger moiety, e.g., “heteroaralkyl”, or “heteroaralkoxy”, refer to groups having 5 to 14 ring atoms; having 6, 10, or 14 ⁇ electrons shared in a cyclic array; and having, in addition to carbon atoms, from one to five heteroatoms.
  • a heteroaryl group may be mono-, bi-, tri-, or polycyclic.
  • heteroatom refers to nitrogen, oxygen and/or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quatenized form of a basic nitrogen.
  • a nitrogen atom of a heteroaryl may be a basic nitrogen atom and may also be optionally oxidized to the corresponding N-oxide.
  • heteroaryl also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocycloaliphatic rings.
  • heteroaryl groups include thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, pteridinyl, indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinoliziny
  • alkylene represents a respective system as described herein, but has two points of attachment to the rest of the molecule.
  • the present invention provides surface modified inorganic nanoparticles, wherein inorganic nanoparticles are surface modified with a surface modifier comprising an organic compound having a refractive index of at least 1.50, and contains at least one functional group capable of forming covalent bond or ligand with the surfaces of the inorganic nanoparticles.
  • the organic compound has at least one group selected from hydroxyl group, carboxyl group, anhydride group, isocyanate group and hydrolysable silane group, so as to interact with and modify the surfaces of the inorganic nanoparticles.
  • the organic compound may also have an optionally substituted aryl or an optionally substituted arylene moiety.
  • inorganic nanoparticles are conventionally surface modified with an organic compound whose RI is not larger than 1.45, and is less than the RI of the inorganic nanoparticles. Since the density of the conventional surface modifier is usually much less than the density of the inorganic particles, the volume of the organic modifier is undesirably large, and thus the volume average density of the inorganic nanoparticles are drastically decreased after being modified, which will in turn decrease the RI value of the surface modified inorganic nanoparticles.
  • the inventors has surprisingly found that by employing organic compounds having high refractive index, such as at least 1.50, the surface modified inorganic nanoparticles and the cured products of adhesive composition containing the surface modified inorganic nanoparticles are provided with higher refractive index values than any current surface modified inorganic nanoparticles which are commercially available.
  • such cured products of adhesive composition containing the surface modified inorganic nanoparticles exhibit high transparency, low haze, yellowness and light stability, and thus the surface modified inorganic nanoparticles are suitable to be used in optical adhesives such as LOCA as additives such as filler.
  • the organic compound is selected from the group consisting of a cumylphenol derivative having at least one hydroxyl group, a phthalate derivative having at least one hydroxyl group, and combination thereof.
  • the cumylphenol derivative having at least one hydroxyl group may be represented by Formula (1) ,
  • R 1 is an optionally substituted alkylene group, an optionally substituted alkenylene group, an optionally substituted aralkylene group, an optionally substituted alkarylene group, an optionally substituted arylene group, an optionally substituted heteroarylene group, and an acyl group.
  • R 1 is an optionally substituted C 1 -C 6 alkylene group.
  • R 1 is a C 1 -C 6 alkylene group substituted by one or two groups selected from ester groups, ether groups, acyl group, hydroxyl group, and carboxyl group.
  • R 1 is a C 1 -C 6 alkylene group substituted by a hydroxyl group or carboxyl group.
  • R 1 is selected from 1-hydroxyl propylene, 2-hydroxyl propylene, and 3-hydroxyl propylene. Preferred is 2-hydroxyl propylene. More preferably, the cumylphenol derivative having at least one hydroxyl group is 3- [4- (1-methyl-1-phenyl-ethyl) -phenoxy] -propane-1, 2-diol.
  • the phthalate derivative is represented by Formula (2)
  • R 2 is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aralkyl group, an optionally substituted alkaryl group, an optionally substituted aryl group, an optionally substituted heteroaryl group and an optionally substituted ester group.
  • R 2 is an optionally substituted C 1 -C 6 alkyl group.
  • R 2 is a C 1 -C 6 alkyl group substituted by one or two groups selected from ester groups, ether groups, acyl group, hydroxyl group, and carboxyl group.
  • R 2 is a C 1 -C 6 alkyl group substituted by an ester group or an ether group.
  • R 2 is selected from the group consisting of (meth) acrylate group, fumate group, maleate group, urethane group, and more preferably is a (meth) acrylate group selected from methyl (meth) acrylate group, ethyl (meth) acrylate group, propyl (meth) acrylate group, butyl (meth) acrylate group, isobutyl (meth) acrylate group, 2-ethyl hexyl (meth) acrylate group, hydroxyethyl (meth) acrylate group, hydroxypropyl (meth) acrylate group, hydroxybutyl (meth) acrylate group, hydroxyhexyl (meth) acrylate group and hydroxyoctyl (meth) acrylate group.
  • R 2 is methyl acrylate or methyl methacrylate group.
  • the phthalate derivative is phthalic acid mono- (2-acryloyloxy
  • the organic compound may be a hydrolysable silane represented by Formula (3)
  • X each independently represents an optionally substituted alkyl; and Q represents an optionally substituted alkyl, an optionally substituted alkoxy, an optionally substituted aryl and/or a hydrolyzate/condensate obtained therefrom.
  • the alkyl group may be linear, branched or cyclic.
  • the linear or branched alkyl group may be, for example, a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, an i-butyl group, a s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group.
  • a preferred linear or branched alkyl group is one having from 1 to 4 carbon atoms.
  • the cycloalkyl group may be, for example, preferably a cyclohexyl group, a cycloheptyl group or a cyclooctyl group.
  • the aryl group may be, for example, a phenyl group.
  • the organic group X represents C 1 -C 4 alkyl and Q represents C 1 -C 8 alkyl, phenyl, methoxy, or ethoxy, and/or a hydrolyzate/condensate obtained therefrom.
  • Suitable substituents may be, for example, a halogen atom (such as a chlorine atom, a bromine atom or a fluorine atom) , a (meth) acryloyl group, a mercapto group, and an alicyclic group.
  • a halogen atom such as a chlorine atom, a bromine atom or a fluorine atom
  • a (meth) acryloyl group such as a chlorine atom, a bromine atom or a fluorine atom
  • hydrolysable silanes of formula (3) include, for example, methyl trimethoxysilane, methyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, n-propyl trimethoxysilane, n-propyl triethoxysilane, i-propyl trimethoxysilane, i-propyl triethoxysilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -chloropropyltriethoxysilane, vinyl trimethoxysilane, vinyl triethoxysilane, 3, 3, 3-trifluoropropyl trimethoxysilane, 3, 3, 3-trifluoropropyl triethoxysilane, cyclohexyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysi
  • the hydrolysable silane comprises alkyltrialkoxysilane or a hydrolyzate/condensate obtained therefrom.
  • Preferred is methyl trimethoxysilane, methyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, n-propyl trimethoxysilane, n-propyl triethoxysilane, and more preferred is n-propyl trimethoxysilane.
  • the surface modifier according to the present invention may optionally further comprise other surface modifier (s) having a monocarboxylic acid end group, and also having a reactive group such as a (meth) acrylate end group.
  • the other surface modifier is carboxyalkyl (meth) acrylate, preferably carboxy C 1 -C 6 alkyl (meth) acrylate.
  • examples are carboxymethyl (meth) acrylate, carboxyethyl (meth) acrylate, carboxybutyl (meth) acrylate.
  • Preferred is ⁇ -carboxyethyl (meth) acrylate.
  • the organic compound is present in an amount from about 5%to about 40%by weight, preferably from about 10%to about 35%by weight, more preferably from about 12%to about 30%by weight, based on the total weight of the surface modified inorganic nanoparticles.
  • the surface modified inorganic particles may exhibit high RI and high light stability while employing only small amount of the organic compound.
  • the surface modified inorganic nanoparticles according to the present invention may be used as fillers in adhesives (especially OCAs and LOCAs) , sealants and/or potting materials.
  • Surface modified inorganic nanoparticles are present in the materials in an amount effective to enhance the durability and/or refractive index of the cured products of the adhesive compositions applied on articles or optical devices.
  • the optical devices or optical articles include wearable display devices, image sensors and light emitting diodes (LEDs) . If used in a curable adhesive composition, the total amount of the surface modified inorganic nanoparticles can be present in an amount from 5%to 90%by weight, preferably from 7%to 85%by weight based on the total weight of the adhesive composition depending on actual needs.
  • the size of such particles is chosen to avoid significant visible light scattering. It may be desirable to employ a mixture of inorganic oxide particle types to optimize an optical or material property and to lower total composition cost.
  • the surface modified nanoparticles can be oxide particles having a (e.g. unassociated) primary particle size or associated particle size of greater than 1 nm, 5 nm or 10 nm.
  • the primary or associated particle size is generally less than 100 nm, 75 nm, or 50 nm. Typically the primary or associated particle size is less than 40 nm, 30 nm, or 20 nm. It is preferred that the nanoparticles are unassociated. Their measurements can be based on transmission electron microscopy (TEM) .
  • TEM transmission electron microscopy
  • nanoparticles can include but not limited to metal oxides such as, ZrO 2 , TiO 2 , Al 2 O 3 , Sb 2 O 4 (or Sb 2 O 3 , Sb 2 O 5 ) , CdO, CaO 2 , Cu 2 O, FeO, Fe 2 O 3 , PbO, MnO, MnO 3 , SnO 2 , ZnO, ZnS, ZnSe, ZnTe and mixtures thereof.
  • metal oxides such as, ZrO 2 , TiO 2 , Al 2 O 3 , Sb 2 O 4 (or Sb 2 O 3 , Sb 2 O 5 ) , CdO, CaO 2 , Cu 2 O, FeO, Fe 2 O 3 , PbO, MnO, MnO 3 , SnO 2 , ZnO, ZnS, ZnSe, ZnTe and mixtures thereof.
  • Surface modified nanoparticles can be substantially fully condensed.
  • Fully condensed inorganic nanoparticles typically have a degree of crystallinity (measured as isolated metal oxide particles) greater than 55%, preferably greater than 60%, and more preferably greater than 70%.
  • the degree of crystallinity can range up to about 86%or greater.
  • the degree of crystallinity can be determined by X-ray diffraction techniques.
  • Condensed crystalline (e.g. zirconia) inorganic nanoparticles have a high refractive index whereas amorphous inorganic nanoparticles typically have a lower refractive index.
  • ZrO 2 , TiO 2 and Al 2 O 3 , nanoparticles are preferred, and can have a particle size from 5 to 50 nm, or from 5 to 15 nm, or from 8 nm to 12 nm.
  • the inorganic nanoparticles can be present in a curable adhesive composition in an amount from 10%to 70%by weight, or from 30%to 60%by weight based on the total weight of the curable adhesive composition.
  • ZrO 2 nanoparticles for use in adhesive composition of the invention are available from Sakai Chemical under the trade designation “SZR” .
  • the surface modification of the inorganic nanoparticles may be dispersed in advance, and can be accomplished in a variety of ways.
  • the dispersing process generally involves the mixture of an inorganic particle dispersion with surface modifier (s) .
  • a solvent for example, toluene, methanol, 1-methoxy-2-propanol, ethanol, isopropanol, ethylene glycol, N, N-dimethylacetamide and 1-methyl-2-pyrrolidinone can be added in the dispersion.
  • the solvent can enhance the solubility of the surface modified particles in the surface modifier.
  • the mixed dispersion comprising the inorganic nanoparticles and surface modifier can be subsequently treated at room or an elevated temperature, with or without mixing.
  • the present application concerns a curable adhesive composition, comprising the surface modified inorganic nanoparticles according to the present invention and a curable resin.
  • the curing mechanism of the adhesive composition may include, not limited to radiation curing, thermal curing, and combination thereof.
  • the curable adhesive composition is a radiation curable, and contains a radiation curable resin.
  • the backbone of the radiation-curable resins is not limited.
  • the reactive functionalities on the resins will be those reactive to the initiators or catalysts formed by exposure to radiation and include, but are not limited to, epoxies, selected from glycidyl epoxy, aliphatic epoxy, and cycloaliphatic epoxy; oxetane; acrylate and methacrylate; itaconate; vinyl, propenyl, crotyl, allyl, and propargyl ether and thio-ethers of those groups; maleate, fumarate, and cinnamate esters; styrenic; acrylamide and methacrylamide; chalcone; epoxy-thiol; and thiol-alkene.
  • More suitable cationic polymerizable radiation-curable resins include epoxies, oxetanes, vinyl ethers, and propenyl ethers.
  • Representative epoxy resins are glycidyl ethers and cycloaliphatic epoxies, which are commercially available from a number of sources known to those skilled in the art.
  • Representative aromatic liquid glycidyl ethers include bisphenol F diglycidyl ether (sold under the trade name Epikote 862 from Resolution Performance Products) or bisphenol A diglycidyl ether (sold under the trade name Epikote 828 from Resolution Performance Products) .
  • Representative solid glycidyl ethers include tetramethylbiphenyl diglycidyl ether (sold under the trade name RSS 1407) and resorcinol diglycidyl ether (sold under the trade name Erisys available from CVC Specialty Chemicals, Inc. ) .
  • Other aromatic glycidyl ethers are commercially available under the trade names Epon 1031, Epon 164, and SU-8 available from Resolution Performance Products.
  • Representative cycloaliphatic epoxy resins include ERL 4221 and ERL 6128 available from Dow Chemical Co.
  • a representative oxetane resin is OXT-121 available from Toagosei.
  • Representative vinyl ether compounds include cyclohexanedimethyloldivinyl ether (Rapicure-CHVE) , tripropylene glycol divinyl ether (Rapicure-DPE-3) or dodecyl vinyl ether (Rapicure-DDVE) all available from International Specialty Products. Analogous vinyl ethers are also available from BASF.
  • Suitable radically polymerizable radiation-curable resins include (meth) acrylates or thiol-ene based resins. In many cases, combinations of the curable resins can be utilized to tailor the properties of the sealant/adhesive material.
  • Representative (meth) acrylate resin includes but not limited to 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, menubutoxy ethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxye
  • the selection of a photoinitiating system for the inventive radiation curable adhesive composition is familiar to those skilled in the art of radiation curing.
  • the photoinitiating system will comprise one or more photoinitiators and optionally one or more photosensitizers.
  • the selection of an appropriate photoinitiator is highly dependent on the specific application in which the barrier sealant is to be used.
  • a suitable photoinitiator is one that exhibits a light absorption spectrum that is distinct from that of the resins, fillers, and other additives in the radiation curable system.
  • the curable adhesive compositions described herein may further comprise one or more flow additives, adhesion promoters, rheology modifiers, toughening agents, fluxing agents, film flexibilizers, UV stabilizers, curing agents, diluent and the like, as well as mixtures of any two or more thereof, as long as the optical properties and other advantages achieved by the adhesive composition are not negatively influenced.
  • the present invention also relates to a cured product of the curable adhesive composition.
  • the cured product has a refractive index of at least 1.60 as defined above.
  • the organic layers were dried over sodium sulfate, followed by concentration in vacuo.
  • the product i.e., Modifier 1
  • the product was purified by column chromatography (ethyl acetate: hexanes, volume ratio being 90: 10) to afford 34.48 g of a clear viscous liquid in 80.3%by weight yield.
  • the resultant Modifier 1 was characterized by NMR: 1 H NMR (CDCl 3 , 300 MHz) , ⁇ (ppm) : 7.34-7.08 (7 H) , 6.85-6.76 (2H) , 4.15-4.04 (1H) , 4.04-3.96 (2H) , 3.96-3.68 (2H) , 1.69-1.62 (6 H) .
  • SMND-4 were prepared in the same way as described above for SMND-1, except that 15.8 g toluene, 0.54 g modifier 2 (available from POLYGON company) , and 10.3 g methanol (with 30%ZrO 2 dispersed in it, obtained from Sakai Chemical) were used.
  • the resultant surface modified ZrO 2 nanoparticles had an organic content (i.e., modifier 2) of the surface modified nanoparticle being 15 %by weight.
  • SMND-5 were prepared in the same way as described above for SMND-1, except that 12.1 g toluene, 0.28 g Modifier 2 (available from POLYGON company) , and 8.3 g methanol (with 30%ZrO 2 dispersed in it, obtained from Sakai Chemical) were used.
  • the resultant surface modified ZrO 2 nanoparticles had an organic content (i.e., Modifier 2) of the surface modified nanoparticle being 10 %by weight.
  • SMND-6 were prepared in the same way as described above for SMND-2, except that acrylic acid was used instead of Modifier 1 and ⁇ -carboxyethylacrylate, and organic content (i.e., acrylic acid) of the surface modified nanoparticle is 20%.
  • SMND-7 were prepared in the same way as described above for SMND-2, except that hydroxyethyl methylacrylate was used instead of Modifier 1 and ⁇ -carboxyethylacrylate, and the organic content (i.e., hydroxyethyl methylacrylate) of the surface modified nanoparticle is 20%.
  • SMND-8 were prepared in the same way as described above for SMND-2, except that citric acid was used instead of Modifier 1 and ⁇ -carboxyethylacrylate, and the organic content (i.e., citric acid) of the surface modified nanoparticle is 20%.
  • Each surface modified nanoparticle dispersion prepared in SMND-1 to 5 and benzyl methacrylate (available from Aldrich Company) were mixed in a 100 ml round bottom flask.
  • the weight parts of the surface modified nanoparticle dispersions were listed in Table 1.
  • the total weight of the surface modified nanoparticle dispersion and benzyl methacrylate added up to 99.9 weight parts.
  • 0.1 weight parts of Igracure 184 (available from BASF) was added into the flask.
  • the solvent contained in the surface modified nanoparticle dispersion was removed at 40°Cby using a rotatory evaporator.
  • the mixture in the form of transparent paste was cured under UV irradiation (50mW/cm 2 ) by a Loctite Zeta Conveyor 7415 for 1 minute.
  • the RI values of the cured products of adhesive composition were measured at room temperature by Metricon refractometer at 589 nm and recorded in Table 1.
  • Each of the paste compositions prepared as described above was dispensed between two pieces of 3 cm X5cm glass with a 300 ⁇ m gap. Then the compositions between glasses were cured under UV (50mW/cm 2 ) by a Loctite Zeta Conveyor 7415for 1 minute.
  • optical properties such as transmittance, haze, and yellow index were tested on a Datacolor 650 instrument available from Datacolor.
  • the adhesive compositions were tested in QUV accelerated weathering tester manufactured by Q-Lab Corporation, which reproduces the damage caused by sunlight, rain and dew. In a few days or weeks, the QUV accelerated weathering tester can reproduce the damage that occurs over months or years outdoors.
  • Benchmark-1 is a surface modified ZrO 2 nanoparticle dispersion commercially available from Nippon Shokubai in the trade name of 153-A.
  • Benchmark-2 is a surface modified ZrO 2 nanoparticle dispersion commercially available from Nippon Shokubai in the trade name of 158-A.
  • Benchmark-3 is a surface modified ZrO 2 nanoparticle dispersion commercially available from Nippon Shokubai in the trade name of 159-A.
  • the inventive adhesive compositions exhibited increased refractive indexes (RIs) than the compositions containing benchmark products of surface modified ZrO 2 nanoparticle dispersion.
  • the inventive adhesive compositions showed comparable or better light stability including initial yellowness, haze and transparency compared to the comparative examples.
  • the inventive adhesive compositions achieved an excellent durability as demonstrated by the QUV accelerated weathering test. Therefore, the nanoparticles surface modified by the inventive modifier are suitable for the use in optical adhesive products, such as LOCA, and could increase the light stability and duration than those of the currently marked products.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne des nanoparticules inorganiques à surface modifiée et leur utilisation. En particulier, l'invention concerne des nanoparticules inorganiques à surface modifiée ayant un indice de réfraction élevé d'au moins 1,50, ainsi que leur utilisation en tant que charges dans des adhésifs, des matériaux d'étanchéité et/ou des matières d'enrobage, en particulier dans des adhésifs optiques transparents (OCA), tels que des adhésifs transparents optiques liquides (LOCA).
PCT/CN2017/091051 2017-06-30 2017-06-30 Nanoparticules inorganiques à surface modifiée et leur utilisation WO2019000375A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009071991A2 (fr) * 2007-12-06 2009-06-11 Henkel Ag & Co. Kgaa Compositions de benzoxazine remplies de silice en nanoparticules
WO2010005710A1 (fr) * 2008-06-16 2010-01-14 3M Innovative Properties Company Compositions durcissables trempées
WO2014005753A1 (fr) * 2012-07-06 2014-01-09 Akzo Nobel Coatings International B.V. Procédé de production d'une dispersion de nanocomposite comprenant des particules composites de nanoparticules inorganiques et des polymères organiques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009071991A2 (fr) * 2007-12-06 2009-06-11 Henkel Ag & Co. Kgaa Compositions de benzoxazine remplies de silice en nanoparticules
WO2010005710A1 (fr) * 2008-06-16 2010-01-14 3M Innovative Properties Company Compositions durcissables trempées
WO2014005753A1 (fr) * 2012-07-06 2014-01-09 Akzo Nobel Coatings International B.V. Procédé de production d'une dispersion de nanocomposite comprenant des particules composites de nanoparticules inorganiques et des polymères organiques

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