Classifications

• • 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
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/12—Esters of monohydric alcohols or phenols
  • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/52—Amides or imides
  • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F20/56—Acrylamide; Methacrylamide
• • 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
  • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
• • 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
  • C08K9/02—Ingredients treated with inorganic 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/011—Nanostructured additives

Definitions

• the present invention relates to a semiconductor nanoparticle-containing curable composition, a cured product, an optical material, and an electronic material. More specifically, the present invention relates to a semiconductor nanoparticle-containing curable composition, a cured product obtained by curing the semiconductor nanoparticle-containing curable composition, and an optical material / electronic material comprising the cured product.
• resin materials as optical materials and electronic materials used for optical parts and electronic parts such as optical lenses, optical elements, optical waveguides, and LED (Light Emitting Diode) sealing materials.
• resin materials used for an LED sealing material there is a phosphor-containing composition containing silica fine particles, a phosphor, and a liquid medium (see, for example, Patent Documents 1 to 4).
• a curable composition which can be used for an LED encapsulant or the like it has silica fine particles, (meth) acrylate having two or more ethylenically unsaturated groups and no ring structure, and having ethylenically unsaturated groups.
• silica fine particles there is one that includes (meth) acrylate having an alicyclic structure and a polymerization initiator, and silica fine particles are surface-treated with a silane compound (for example, see Patent Document 5).
• Patent Document 6 describes a liquid curable resin composition containing an inorganic phosphor and a nanoparticle phosphor composed of a hydrocarbon group coordinated to the inorganic phosphor.
• compositions containing nano-sized semiconductor particles have problems such as poor dispersibility of semiconductor nanoparticles and insufficient handling properties.
• the present invention has been made in view of the above circumstances, and includes a semiconductor nanoparticle that is a luminescent material and has excellent handling properties and dispersibility, a cured product obtained by curing the composition, and It is an object to provide an optical material / electronic material made of the cured product.
• the present inventors diligently studied to solve the above problems. As a result, excellent handling is achieved by forming a curable composition containing a specific alkyl (meth) acrylate compound, a specific (meth) acrylamide compound, a polymerization initiator, and semiconductor nanoparticles that are light emitters.
• the present invention has been conceived by finding that the property and dispersibility can be obtained.
• the present invention employs the following configuration.
• R 1 represents a methyl group or a hydrogen atom
• R 2 represents a linear or branched alkyl group having 8 to 22 carbon atoms.
• R 3 represents a methyl group or a hydrogen atom
• R 4 represents a linear alkylene group having 1 to 6 carbon atoms.
• the ethylenically unsaturated group-containing compound (e) is converted into 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-vinylpyrrolidone, N- Vinyl- ⁇ caprolactam, ⁇ -butyrolactone (meth) acrylate, N-acryloylmorpholine, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N-vinylformamide, N-vinylacetamide, methyl-2-allyloxymethyl acrylate, tetrahydrafurfuryl acrylate, ethylene oxide adduct di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) Acrylate, ethylene glycol diacrylate, semiconductor nanoparticle-containing cur
• the semiconductor nanoparticle (d) has a nanoparticle core containing ions of at least one element selected from the group consisting of Groups 3 to 16 of the periodic table [1]
• the semiconductor nanoparticle-containing curable composition according to any one of [3] to [3].
• the nanoparticle core is made of the group consisting of ZnS, ZnSe, ZnTe, InP, InAs, InSb, AlS, AlAs, AlSb, GaN, GaP, GaAs, GaSb, PdS, PbSe, Si, Ge, MgSe, and MgTe.
• the curable composition containing semiconductor nanoparticles according to [4] comprising at least one selected.
• the semiconductor nanoparticle (d) includes a nanoparticle core and a capping layer having a protective group coordinated to the surface of the nanoparticle core, and the surface of the nanoparticle core is made of an inorganic material.
• the curable composition containing semiconductor nanoparticles according to any one of [1] to [5], wherein the curable composition is coated with a single shell.
• the content of the alkyl (meth) acrylate compound (a) in the semiconductor nanoparticle-containing curable composition is 5 to 40% by mass, and the content of the (meth) acrylamide compound (b) is 30 to 90.
• the semiconductor nanoparticle-containing curable composition according to any one of [1] to [7], further comprising a (meth) acrylate compound (f) having two or more (meth) acrylate groups in the molecule. .
• the (meth) acrylate (f) is trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol.
• the semiconductor nanoparticle according to [8] which is at least one selected from penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and trimethylolpropane trioxyethyl (meth) acrylate Containing curable composition.
• An optical material comprising the cured product according to [10].
• An electronic material comprising the cured product according to [10].
• the semiconductor nanoparticle-containing curable composition of the present invention includes a specific alkyl (meth) acrylate compound, a specific (meth) acrylamide compound, a polymerization initiator, and semiconductor nanoparticles that are light emitters.
• the semiconductor nanoparticle containing curable composition of this invention can utilize the light wavelength conversion effect
• cured material which can be used conveniently for an optical material and an electronic material is obtained by hardening the semiconductor nanoparticle containing curable composition of this invention.
• nanoparticle-containing curable composition of the present invention
• a cured product obtained by curing the nanoparticle-containing curable composition and
• the optical material / electronic material made of the cured product will be described in detail.
• the material, dimension, etc. which are illustrated in the following description are examples, and this invention is not limited to them.
• the present invention can be appropriately modified and implemented without changing the gist thereof.
• the nanoparticle-containing curable composition of the present invention comprises an alkyl (meth) acrylate compound (a) represented by the above general formula (1) (hereinafter also referred to as “(meth) acrylate (a)”) and the above general formula ( 2) (meth) acrylamide compound (b) (hereinafter, also referred to as “(meth) acrylamide (b)”), a polymerization initiator (c), and semiconductor nanoparticles (d) that are light emitters. .
• the nanoparticle-containing curable composition of the present invention contains semiconductor nanoparticles (d) that are light emitters, the light wavelength conversion action by the semiconductor nanoparticles can be obtained. Therefore, the nanoparticle-containing curable composition of the present invention can be preferably used for optical parts and electronic parts such as optical lenses, optical elements, optical waveguides, and LED sealing materials.
• the “(meth) acrylate compound” means an acrylate compound and / or a methacrylate compound.
• the “(meth) acrylamide compound” means an acrylamide compound and / or a methacrylamide compound.
• (Meth) acrylate (a) is a compound represented by the following general formula (1).
• R 1 represents a methyl group or a hydrogen atom
• R 2 represents a linear or branched alkyl group having 8 to 22 carbon atoms.
• R 1 is a hydrogen atom
• R 2 preferably has 8 to 15 carbon atoms, and more preferably 8 to 13 carbon atoms, in order to further improve the dispersibility of the semiconductor nanoparticles.
• R 2 is preferably linear because it can further improve the dispersibility of the semiconductor nanoparticles.
• (meth) acrylate (a) is contained in the nanoparticle-containing curable composition, a cured product having excellent dispersibility of the semiconductor nanoparticles can be obtained.
• (meth) acrylate (a) include n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, isotridecyl (meth) acrylate, lauryl (meth) acrylate , Stearyl (meth) acrylate, isostearyl (meth) acrylate, and the like.
• Said (meth) acrylate (a) may be used independently and may use 2 or more types together.
• the content of (meth) acrylate (a) in the nanoparticle-containing curable composition is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass.
• the content ratio of (meth) acrylate (a) and (meth) acrylamide (b) is good.
• a product can be easily obtained, and a nanoparticle-containing curable composition with further excellent dispersibility of semiconductor nanoparticles can be easily obtained.
• ⁇ (Meth) acrylamide (b)> (Meth) acrylamide (b) is liquid. Dispersibility of semiconductor nanoparticles in the nanoparticle-containing curable composition is improved by including (meth) acrylamide (b) together with (meth) acrylate (a) in the nanoparticle-containing curable composition. In addition, sedimentation of the semiconductor nanoparticles can be prevented. For this reason, the nanoparticle containing curable composition of this embodiment can utilize effectively the light wavelength conversion effect
• (Meth) acrylamide (b) has an acrylamide group or a methacrylamide group and a hydroxyl group in the molecule, and is a compound represented by the following general formula (2).
• R 3 represents a methyl group or a hydrogen atom
• R 4 represents an alkylene group having 1 to 6 carbon atoms.
• R 4 preferably has 1 to 3 carbon atoms, and more preferably 2 carbon atoms so that a composition having excellent dispersibility can be formed.
• R 3 is a hydrogen atom
• a nanoparticle-containing curable composition having a high curing rate is obtained, which is preferable.
• N-hydroxyethylacrylamide is most preferable.
• the content of (meth) acrylamide (b) in the nanoparticle-containing curable composition is preferably 30 to 90% by mass, and more preferably 40 to 80% by mass.
• the content ratio of (meth) acrylate (a) and (meth) acrylamide (b) is good and the nanoparticle-containing curable composition A product can be easily obtained, and a nanoparticle-containing curable composition with further excellent dispersibility of semiconductor nanoparticles can be easily obtained.
• the polymerization initiator (c) contributes to the curing of the nanoparticle-containing curable composition.
• the polymerization initiator (c) include a photopolymerization initiator that generates radicals and a thermal polymerization initiator.
• the photopolymerization initiator include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxy-phenylphenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, diphenyl- (2,4,6-trimethyl). Benzoyl) phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Two or more of these photopolymerization initiators may be used in combination.
• the content of the polymerization initiator (c) in the nanoparticle-containing curable composition may be an amount that can appropriately cure the nanoparticle-containing curable composition.
• the content of the polymerization initiator (c) with respect to the total mass of the monomer and the semiconductor nanoparticles (d) in the semiconductor nanoparticle-containing curable composition is preferably 0.01 to 10% by mass, more preferably It is 0.02 to 5% by mass, and more preferably 0.1 to 2% by mass. When there is too much content of a polymerization initiator, the storage stability of a nanoparticle containing curable composition may fall or it may color.
• the monomer in the semiconductor nanoparticle-containing curable composition means (meth) acrylate (a), (meth) acrylamide (b), ethylenically unsaturated group-containing compound (e), (meth) acrylate (f). To do.
• thermal polymerization initiator examples include benzoyl peroxide, diisopropyl peroxycarbonate, t-butyl peroxy (2-ethylhexanoate), t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbo Nate, dilauroyl peroxide, diisopropyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane Can be mentioned. These thermal polymerization initiators may be used alone or in combination of two or more.
• the semiconductor nanoparticle (d) is a light emitter.
• the semiconductor nanoparticles (d) those having a number average particle diameter of 1 nm to 1000 nm are preferably used.
• the number average particle size of the semiconductor nanoparticles (d) is more preferably less than 20 nm, and even more preferably less than 15 nm.
• the number average particle diameter of the semiconductor nanoparticles (d) is most preferably 2 to 5 nm.
• the semiconductor nanoparticle (d) becomes a phosphor having a quantum dot effect that quantum confines electrons of the semiconductor nanoparticle (d).
• the semiconductor nanoparticle (d) preferably includes a nanoparticle core and a capping layer having a protective group coordinated on the surface of the nanoparticle core.
• the protecting group consists of a hydrocarbon group.
• the nanoparticle core of the semiconductor nanoparticle (d) contains ions.
• the ions contained in the nanoparticle core are not particularly limited, and preferably include ions of at least one element selected from the group consisting of Groups 3 to 16 of the periodic table.
• the nanoparticle core contains ions of two or more kinds of elements
• the first ion is an ion of at least one element selected from the group consisting of Groups 11 to 14 of the periodic table.
• the second ion is an ion of at least one element selected from the group consisting of Groups 14 to 16 of the periodic table.
• the nanoparticle core includes a semiconductor material.
• Semiconductor materials used for the nanoparticle core include ZnS, ZnSe, ZnTe, InP, InAs, InSb, AlS, AlAs, AlSb, GaN, GaP, GaAs, GaSb, PbS, PbSe, Si, Ge, MgSe, MgTe, and CdS. , CdSe, CdTe, CdO, AlP, MgS, and ZnO.
• semiconductor materials used for the nanoparticle core ZnS, ZnSe, ZnTe, InP, InAs, InSb, AlS, AlAs, AlSb, GaN, GaP, GaAs, GaSb, PdS, PbSe, Si, Ge, MgSe, It is preferable to include at least one selected from the group consisting of MgTe.
• the semiconductor nanoparticle (d) is preferably a core-shell type in which the surface of the nanoparticle core is covered with a shell made of an inorganic material.
• the shell may be composed of one layer, or may be composed of two or more layers (core-multishell type).
• core-multishell type the bonding between the nanoparticle core and the protective group is promoted by the shell, so that an excellent quantum dot effect can be obtained.
• the semiconductor nanoparticles (d) may be doped nanoparticles or tilted nanoparticles.
• the content of the semiconductor nanoparticles (d) in the nanoparticle-containing curable composition is preferably 0.1 to 20% by mass.
• the content of the semiconductor nanoparticles (d) in the nanoparticle-containing curable composition is 0.1% by mass or more, the light wavelength conversion action by containing the semiconductor nanoparticles (d) is more effective. can get. Therefore, the hardened
• cured material will be excellent in the compounding quantity of a semiconductor nanoparticle (d) being 20 mass% or less.
• the semiconductor nanoparticles (d) can adjust the emission wavelength of the semiconductor nanoparticles (d) by changing the number average particle diameter and the material of the nanoparticle core. Therefore, for example, by applying a nanoparticle-containing curable composition containing semiconductor nanoparticles (d) to the LED surface and curing the LED, the LED emits white light by the action of light wavelength conversion of the semiconductor nanoparticles (d). Can be manufactured.
• the nanoparticle-containing curable composition of the present invention comprises an ethylenically unsaturated group-containing compound (e) (hereinafter referred to as an “ethylenically unsaturated group-containing compound) dissolved in (meth) acrylate (a) and (meth) acrylamide (b). (E) "is also preferably included.
• the ethylenically unsaturated group-containing compound (e) excludes (meth) acrylate (a), (meth) acrylamide (b), and (meth) acrylate (f).
• dissolved in (meth) acrylate (a) is defined as follows.
• the ethylenically unsaturated group-containing compound (e) corresponding to 25 is mixed with the (meth) acrylate (a) 75 in a mass ratio, stirred at 2000 rpm for 60 seconds by a rotating and rotating stirrer, and allowed to stand for 24 hours
• the volume amount of the ethylenically unsaturated group-containing compound (e) dissolved in the (meth) acrylate (a) is 90% or more of the total ethylenically unsaturated group-containing compound (e).
• dissolving in (meth) acrylamide (b) is defined as follows in the same manner as “dissolving in (meth) acrylate (a)”.
• ethylenically unsaturated group-containing compound (e) corresponding to 25 is mixed with (meth) acrylamide (b) 75 in a mass ratio, stirred at 2000 rpm for 60 seconds with a rotating and rotating stirrer, and then allowed to stand for 24 hours
• the volume amount of the ethylenically unsaturated group-containing compound (e) dissolved in (meth) acrylamide (b) is 90% or more of the total ethylenically unsaturated group-containing compound (e).
• the nanoparticle-containing curable composition contains the ethylenically unsaturated group-containing compound (e)
• the dispersibility of the semiconductor nanoparticles in the nanoparticle-containing curable composition is improved, and the semiconductor nanoparticles are precipitated over a long period of time. Can be prevented.
• substrate is obtained because the nanoparticle containing curable composition contains the ethylenically unsaturated group containing compound (e).
• Examples of the ethylenically unsaturated group-containing compound (e) include those having a (meth) acrylate group, an acrylamide group, a vinyl group, and an ethylene bond in the molecule, and among them, those having a (meth) acrylate group. preferable.
• ethylenically unsaturated group-containing compound (e) examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, N-vinylpyrrolidone, N-vinyl- ⁇ caprolactam, N-vinylformamide, N-vinylacetamide, N-acryloylmorpholine, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N- [3- (dimethylamino) Propyl] acrylamide, dimethylaminopropylacrylamide, ethylene oxide adduct di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, methyl-2-allyloxymethyl acrylate, ⁇ -butyrolactone Meth) acrylate, tetra hydra furfuryl acrylate, and ethylene glyco
• the content of the ethylenically unsaturated group-containing compound (e) in the nanoparticle-containing curable composition is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass.
• the content of the ethylenically unsaturated group-containing compound (e) is 10% by mass or more, the effect of containing the ethylenically unsaturated group-containing compound (e) can be sufficiently obtained, and the dispersibility of the semiconductor nanoparticles can be obtained. Is higher.
• the content of the ethylenically unsaturated group-containing compound (e) is 30% by mass or less, it becomes easy to secure the contents of (meth) acrylate (a) and (meth) acrylamide (b).
• a nanoparticle-containing curable composition with further excellent particle dispersibility is easily obtained.
• the nanoparticle-containing curable composition of the present invention may further include a (meth) acrylate compound (f) (hereinafter referred to as “(meth) acrylate (f)” having two or more (meth) acrylate groups in the molecule, if necessary. ").
• (meth) acrylate (f) excludes (meth) acrylate (a), (meth) acrylamide (b), and ethylenically unsaturated group-containing compound (e).
• the (meth) acrylate (f) can increase the degree of crosslinking in a cured product obtained by curing a nanoparticle-containing curable composition containing the (meth) acrylate (f). Therefore, the crosslinking degree of hardened
• (meth) acrylate (f) those having 3 to 4 (meth) acrylate groups in the molecule are preferable, and those having three (meth) acrylate groups in the molecule are more preferable.
• (meth) acrylate (f) includes trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, and the like can be used.
• the (meth) acrylate (f) it is particularly preferable to use trimethylolpropane tri (meth) acrylate because a cured product having an appropriate degree of crosslinking can be produced and the raw material is easily available. .
• the content of (meth) acrylate (f) in the nanoparticle-containing curable composition is preferably 1 to 30% by mass, and more preferably 1 to 10% by mass.
• content of (meth) acrylate (f) is 1% by mass or more, crosslinking with (meth) acrylate (f) proceeds well.
• cured material which has moderate crosslinking degree as content of (meth) acrylate (f) is 30 mass% or less.
• the nanoparticle-containing curable composition of the present invention has characteristics such as dispersibility of the semiconductor nanoparticles (d), viscosity of the composition, and transparency and heat resistance of the cured product as necessary.
• the nanoparticle containing curable composition of this invention does not contain an organic solvent and water substantially.
• the term “substantially” as used herein means that it is not necessary to go through the step of removing the solvent again when actually obtaining a cured product using the nanoparticle-containing curable composition of the present invention.
• “substantially free of organic solvent and water” means that the remaining amount of each of the organic solvent and water in the nanoparticle-containing curable composition is preferably 2% by mass or less, more preferably 1% by mass. % Or less.
• polymerization inhibitor examples include hydroquinone, hydroquinone monomethyl ether, benzoquinone, pt-butylcatechol, 2,6-di-t-butyl-4-methylphenol, and the like. These can be used alone or in combination of two or more.
• leveling agents include polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, polyether-modified methylalkylpolysiloxane copolymer, aralkyl-modified methylalkylpolysiloxane copolymer, and polyether-modified. Examples thereof include methylalkylpolysiloxane copolymer. These can be used alone or in combination of two or more.
• the nanoparticle containing curable composition of this invention can be manufactured by performing the process 1 and the process 2 which are shown below in order, for example.
• Step 1 Metal acrylate (a) and semiconductor nanoparticles (d) are mixed, and volatile components are distilled off (desolvation) to obtain a nanoparticle-containing composition.
• Step 2 A nanoparticle-containing composition obtained in Step 1, (meth) acrylamide (b), a polymerization initiator (c), and, if necessary, an ethylenically unsaturated group-containing compound (e). Mix to obtain a curable composition containing nanoparticles.
• Step 2 A nanoparticle-containing composition obtained in Step 1, (meth) acrylamide (b), a polymerization initiator (c), and, if necessary, an ethylenically unsaturated group-containing compound (e).
• the semiconductor nanoparticles (d) added to the (meth) acrylate (a) are dispersions in which the semiconductor nanoparticles (d) are dispersed in an organic solvent from the viewpoint of dispersibility in the nanoparticle-containing curable composition. It is preferable to use a body.
• the organic solvent in which the semiconductor nanoparticles (d) are dispersed include benzene, xylene, toluene, and the like.
• step 1 semiconductor nanoparticles (d) are added to (meth) acrylate (a) and mixed, and if necessary, the solvent is removed to obtain a nanoparticle-containing composition containing semiconductor nanoparticles (d). obtain.
• a nanoparticle-containing composition containing semiconductor nanoparticles (d).
• (meth) acrylate (f) and / or a dispersion aid are added as necessary. May be.
• the solvent is removed.
• the temperature of the mixed solution containing (meth) acrylate (a) and semiconductor nanoparticles (d) during solvent removal is preferably maintained at 20 to 100 ° C. From the point of balance between the prevention of aggregation and gelation of the nanoparticle-containing curable composition and the solvent removal speed, the temperature of the mixed solution containing (meth) acrylate (a) and semiconductor nanoparticles (d) at the time of solvent removal is More preferably, it is 30 to 70 ° C., and further preferably 30 to 50 ° C.
• the temperature of the mixed solution is preferably set to a temperature not higher than the boiling point of (meth) acrylates contained in the mixed solution. If the temperature of the mixed solution of (meth) acrylate (a) and semiconductor nanoparticles (d) is too high, the fluidity of the nanoparticle-containing curable composition may be extremely lowered or become a gel. Sometimes.
• the nanoparticle-containing composition after desolvation contains substantially no organic solvent and water.
• the term “substantially” as used herein means that it is not necessary to go through the step of removing the solvent again when actually obtaining a cured product using the nanoparticle-containing curable composition of the present invention.
• “substantially free of organic solvent and water” means that the remaining amount of each of the organic solvent and water in the nanoparticle-containing composition is preferably 2% by mass or less, more preferably 1% by mass or less. It means that.
• step 2 the nanoparticle-containing composition obtained in step 1, (meth) acrylamide (b), a polymerization initiator (c), and, if necessary, an ethylenically unsaturated group-containing compound (e), Mix with other ingredients.
• a mixing method For example, the method of mixing each said component with mixers, such as a mixer, a ball mill, and rotation revolution stirring under room temperature or a heating condition, is mentioned. By this method, a nanoparticle-containing curable composition is formed.
• the nanoparticle-containing curable composition obtained in step 2 may be filtered. This filtration is performed in order to remove foreign substances such as dust in the nanoparticle-containing curable composition.
• the filtration method is not particularly limited, but it is preferable to use a pressure filtration method using a membrane type or cartridge type filter having a pore diameter of 10 ⁇ m.
• the nanoparticle-containing curable composition of the present invention can be produced.
• the nanoparticle-containing curable composition of the present invention can utilize the light wavelength conversion action by containing the semiconductor nanoparticles (d).
• the nanoparticle-containing curable composition has a low viscosity even when it does not contain a solvent, and has excellent dispersibility and good handling properties. This is because the nanoparticle-containing curable composition of the present invention comprises a semiconductor nanoparticle (d) which is a light emitter, (meth) acrylate (a) and (meth) acrylamide (b), and a mixture thereof. This is because the semiconductor nanoparticles (d) can be easily dispersed by mixing and stirring. Furthermore, when the nanoparticle containing curable composition of this invention contains an ethylenically unsaturated group containing compound (e), precipitation of a semiconductor nanoparticle can be prevented over a long period of time.
• the cured product of the present invention can be obtained by curing the nanoparticle-containing curable composition of the present invention. Therefore, the cured product of the present invention can utilize the light wavelength conversion action by containing the semiconductor nanoparticles (d), and can be used for optical lenses, optical disk substrates, plastic substrates for liquid crystal display elements, color filter substrates, organic EL display elements. It can be suitably used as an optical material / electronic material such as a plastic substrate, a solar cell substrate, a touch panel, an optical element, an optical waveguide and an LED sealing material.
• cured material of this invention has the process of hardening the nanoparticle containing curable composition of this invention.
• a curing method for example, there are a method of crosslinking a (meth) acryloyloxy group by irradiation of active energy rays, a method of thermally polymerizing a (meth) acryloyloxy group by performing a heat treatment, and these may be used in combination. it can.
• the photopolymerization initiator is added as a polymerization initiator (c) in the nanoparticle-containing curable composition in the above step 2.
• a thermal polymerization initiator is contained as a polymerization initiator (c) in the nanoparticle-containing curable composition.
• the nanoparticle-containing curable composition of the present invention is applied onto a substrate such as a glass plate, a plastic plate, a metal plate, or a silicon wafer to form a coating film. Thereafter, the coating film is obtained by irradiating the coating film with active energy rays and / or heating and curing the coating film.
• Examples of the method for applying the nanoparticle-containing curable composition include application by a bar coater, applicator, die coater, spin coater, spray coater, curtain coater or roll coater, application by screen printing, and application by dipping. Can be mentioned.
• the coating amount of the nanoparticle-containing curable composition of the present invention on the substrate is not particularly limited, and can be appropriately adjusted according to the purpose.
• the coating amount of the nanoparticle-containing curable composition on the substrate is preferably such that the film thickness of the coating film obtained after the curing treatment by irradiation with active energy rays and / or heating is 1 ⁇ m to 10 mm. Is more preferred.
• the active energy ray used for curing the nanoparticle-containing curable composition is preferably an electron beam or light in the ultraviolet to infrared wavelength range.
• the light source for example, an ultra-high pressure mercury light source or a metal halide light source can be used for ultraviolet rays, a metal halide light source or a halogen light source can be used for visible rays, and a halogen light source can be used for infrared rays.
• a light source such as a laser or LED can be used.
• the irradiation amount of the active energy ray is appropriately set according to the type of light source, the film thickness of the coating film, and the like.
• the nanoparticle-containing curable composition may be further cured by heat treatment (annealing treatment).
• the heating temperature is preferably in the range of 50 to 150 ° C.
• the heating time is preferably in the range of 5 to 60 minutes.
• the heating temperature is preferably in the range of 40 to 200 ° C, more preferably in the range of 50 to 150 ° C.
• the heating temperature is lower than the above range, it is necessary to lengthen the heating time, and the economy tends to be lacking. If the heating temperature exceeds the above range, energy costs are required, and further, the heating temperature rise time and the temperature drop time are required.
• the heating time is appropriately set according to the heating temperature, the film thickness of the coating film, and the like.
• the nanoparticle-containing curable composition may be further cured by performing a heat treatment (annealing treatment).
• the heating temperature at that time is preferably in the range of 50 to 150 ° C.
• the heating time is preferably in the range of 5 minutes to 60 minutes.
• RED-CFQD-G2-604 manufactured by NANOCO TECHNOLOGIES, toluene solution with a semiconductor nanoparticle content of 10% by mass, nanoparticle core (InP) shell (ZnS), number average particle size 3-4 nm)
• GREEN-CFQD-G3-525 manufactured by NANOCO TECHNOLOGIES, toluene solution with 10% by mass of semiconductor nanoparticles, nanoparticle core (InP) shell (ZnS), number average particle diameter of 2 to 3 nm
• Ethylenically unsaturated group-containing compound (e) HEA: 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) HPA: 2-hydroxypropyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 4HBA: 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• NVP N-vinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.)
• NVC N-vinylcaprolactam (manufactured by Tokyo Chemical Industry Co., Ltd.)
• GBLMA ⁇ -butyrolactone methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• ACMO N-acryloylmorpholine (manufactured by Kojin Film & Chemicals Co., Ltd.)
• DEAA N-diethylacrylamide (manufact
• TMPTA Trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd.)
• APG700 Propylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
• V # 360 Trimethylolpropane ethylene oxide adduct triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• A9300-1CL Caprolactam-modified tris (acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
• MA Methyl acrylate (Mitsubishi Chemical Corporation)
• Example 1 ⁇ Preparation of nanoparticle-containing curable composition> The flask was charged with 18.75 g of LA and 3.75 g of TMPTA, 1.3 g of RED-CFQD-G2-604 (10% by mass toluene dispersion) as semiconductor nanoparticles (d), GREEN-CFQD-G3-525 ( 23.7 g of 10 mass% toluene dispersion) was added and mixed to obtain a nanoparticle-containing composition containing semiconductor nanoparticles (d). Thereafter, the nanoparticle-containing composition containing the semiconductor nanoparticles (d) was heated under reduced pressure at 40 ° C. and 100 kPa with stirring to remove volatile components.
• nanoparticle-containing composition containing semiconductor nanoparticles (d) from which volatiles have been removed 56.25 g of HEAA and 18.75 g of HEA, 0.5 g of Irgacure 184 as a photopolymerization initiator and 0.1 g of Irgacure 819 are added, The mixture was stirred at 2000 rpm for 60 seconds with a rotation and revolution stirrer to obtain the nanoparticle-containing curable composition of Example 1.
• Example 1 except that the amount of HEAA used was reduced to 56.25 g as described in Tables 1 and 2 and the amount was changed to another (meth) acrylate or an ethylenically unsaturated group-containing compound (e).
• e ethylenically unsaturated group-containing compound
• the nanoparticle-containing curable compositions of Examples 1 to 12 had good dispersibility.
• the liquid was kept in a single layer state even after standing for 48 hours, and exhibited better dispersibility.

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• 2015
  • 2015-05-20 JP JP2016525761A patent/JPWO2015186521A1/ja active Pending
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