WO2017073684A1 - Composition aqueuse de dispersion de résine contenant des particules de composé de métal alcalino-terreux - Google Patents

Composition aqueuse de dispersion de résine contenant des particules de composé de métal alcalino-terreux Download PDF

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WO2017073684A1
WO2017073684A1 PCT/JP2016/081923 JP2016081923W WO2017073684A1 WO 2017073684 A1 WO2017073684 A1 WO 2017073684A1 JP 2016081923 W JP2016081923 W JP 2016081923W WO 2017073684 A1 WO2017073684 A1 WO 2017073684A1
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aqueous resin
resin dispersion
earth metal
alkaline earth
metal compound
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PCT/JP2016/081923
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English (en)
Japanese (ja)
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太一 秋山
里花 野北
武史 日元
中野　博之
高橋　毅
有紀 溝川
拓馬 酒井
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宇部興産株式会社
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Priority to JP2017547862A priority Critical patent/JP6729598B2/ja
Publication of WO2017073684A1 publication Critical patent/WO2017073684A1/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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to an aqueous resin dispersion composition containing alkaline earth metal compound particles and an aqueous resin dispersion.
  • strontium titanate powder is manufactured by mixing a strontium carbonate powder and a titanium dioxide powder to form a powder mixture, followed by firing.
  • Dielectric ceramic powder is used as a constituent material of a dielectric ceramic layer of a multilayer ceramic capacitor.
  • Patent Document 2 discloses that acicular strontium carbonate particles are stretched in a specific polymer resin such as COP (cyclic polyolefin) or PMMA (polymethyl methacrylate), and the extending direction (longitudinal direction) of the binding chain of the polymer resin. And the long axis direction (longitudinal direction) of the acicular strontium carbonate particles are disclosed to be parallel or perpendicular to each other.
  • COP cyclic polyolefin
  • PMMA polymethyl methacrylate
  • strontium carbonate is also known to have, for example, radio wave absorption performance and radiation control functions.
  • strontium carbonate which is an example of an alkaline earth metal compound, has been studied as a constituent material of a dielectric ceramic layer of a multilayer ceramic capacitor and an optical material for controlling optical properties.
  • strontium carbonate which is an example of an alkaline earth metal compound
  • further application expansion is desired.
  • An object of the present invention is to provide a novel resin composition imparted with functionality by alkaline earth metal compound particles such as strontium carbonate.
  • This embodiment (1) relates to an aqueous resin dispersion composition comprising alkaline earth metal compound particles and an aqueous resin dispersion.
  • This aspect (2) relates to the aqueous resin dispersion composition of this aspect (1), wherein the alkaline earth metal compound particles include strontium carbonate particles.
  • This aspect (3) relates to the aqueous resin dispersion composition of this aspect (1) or (2), wherein the aqueous resin is a polyurethane resin.
  • the aqueous resin dispersion composition is at least one of the active energy ray-curable composition and the thermosetting composition.
  • the present invention relates to a resin dispersion composition.
  • the average major axis of the alkaline earth metal compound particles is 100 nm or less, and the average aspect ratio of the alkaline earth metal compound particles is in the range of 1.0 to 5.0.
  • the invention relates to the aqueous resin dispersion composition according to any one of (4) to (4).
  • This aspect (6) relates to the aqueous resin dispersion composition according to any one of the present aspects (1) to (5), wherein a surfactant is applied to the surface of the alkaline earth metal compound particles.
  • any one of the present aspects (1) to (6), wherein the weight of the alkaline earth metal compound particles relative to the solid content of the aqueous resin dispersion composition is 2.5% by mass or more.
  • This aspect (8) relates to a coating composition containing the aqueous resin dispersion composition according to any one of the present aspects (1) to (7).
  • This aspect (9) relates to a coating agent composition containing the aqueous resin dispersion composition according to any one of the present aspects (1) to (7).
  • This aspect (10) relates to an optical resin material containing the aqueous resin dispersion composition according to any one of the present aspects (1) to (7).
  • This aspect (11) relates to a coating film formed from the aqueous resin dispersion composition according to any one of the present aspects (1) to (7).
  • the alkaline earth metal compound particles in one embodiment are mainly composed of alkaline earth metal.
  • the average major axis of the alkaline earth metal compound particles is not particularly limited, but in the present application, the alkaline earth metal compound particles are defined as including nanoparticles or fine particles having an average major axis of, for example, 500 nm or less.
  • the average major axis can be measured by visually or image-processing a scanning electron microscope (SEM) photograph of alkaline earth metal compound particles.
  • the major axis of the alkaline earth metal compound particles can be measured as the length in the longitudinal direction (long side length) when the alkaline earth metal compound particles such as strontium carbonate particles are regarded as rectangular.
  • the short diameter of the alkaline earth metal compound particles can be measured as the length in the short direction (length of the short side) when the alkaline earth metal compound particles are regarded as rectangular.
  • a rectangle having the smallest area circumscribing the alkaline earth metal compound particles is calculated, and the major axis and minor axis are obtained from the length of the long side and the short side of the rectangle.
  • “average” means an average value obtained by measuring a number of statistically reliable (N number) alkaline earth metal compound particles.
  • the number (N number) is usually 300 or more, preferably 500 or more, more preferably 1000 or more.
  • the average aspect ratio of the alkaline earth metal compound particles is not particularly limited, but may be in the range of 1.0 to 5.0, for example.
  • the aspect ratio here means “major axis / minor axis” of the particle.
  • the average aspect ratio means an average aspect ratio. That is, the average aspect ratio is calculated by measuring the aspect ratio of a plurality of particles and calculating the average value of the aspect ratios obtained from the plurality of particles. The number of particles (N number) for calculating the average value is as described above.
  • alkaline earth metal compound particles examples include alkaline earth metal carbonates, sulfates, nitrates, oxides, chlorides, hydroxides, and the like.
  • alkaline earth metal examples include calcium, strontium, barium, and radium. Therefore, examples of the alkaline earth metal compound particles include calcium carbonate particles, strontium carbonate particles, and barium carbonate particles.
  • the alkaline earth metal compound particles are preferably strontium carbonate particles from the viewpoints of various uses such as radio wave absorption use, radiation control use, and / or optical use.
  • a surfactant adheres to the strontium carbonate particles described above. Thereby, the dispersibility of the strontium carbonate particles in the resin composition or in the solvent before mixing in the resin composition can be improved.
  • the type of the surfactant is not particularly limited, but an anionic surfactant is preferable.
  • the anionic surfactant is more preferably a compound containing a hydrophilic group and a hydrophobic group and having a group that forms an anion in water.
  • the hydrophilic group is preferably a polyoxyalkylene group containing an oxyalkylene group having 1 to 8 carbon atoms.
  • the hydrophobic group is preferably an alkyl group or an aryl group.
  • the alkyl group and / or aryl group may have a substituent.
  • the number of carbon atoms of the alkyl group is preferably 3 to 30, and more preferably 10 to 18.
  • the aryl group may have 6 to 30 carbon atoms.
  • the hydrogen atom contained in these acid groups may be substituted with an alkali metal ion such as sodium or potassium or an ammonium ion.
  • the surfactant is a polycarboxylic acid-based anionic surfactant or polyphosphoric acid-based anionic type.
  • a surfactant is preferred.
  • the surfactant is more preferably a polycarboxylic acid-based anionic surfactant.
  • polycarboxylic acid-based anionic surfactant examples include compounds represented by the following formula (I).
  • R 1 means a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
  • E 1 represents an alkylene group having 1 to 8 carbon atoms.
  • A means a positive number in the range of 1 to 20, preferably 2 to 6.
  • R 1 means 10 or more carbon atoms, preferably in the range of 10 to 18. It is preferably an alkyl group in
  • polyphosphoric anionic surfactant examples include a compound represented by the following formula (II) (mono-form), a compound represented by the following formula (III) (di-form), or a formula (II). Mention may be made of a mixture of the compound and the compound represented by the formula (III).
  • R 2 is a substituted or unsubstituted alkyl group, or means a substituted or unsubstituted aryl group.
  • E 2 is an alkylene group in which carbon atoms in the range of 1-8 “B” means a positive number in the range of 1 to 20, preferably 2 to 6.
  • R 2 means a number of carbon atoms of 10 or more, preferably in the range of 10 to 18. It is preferable that it is an alkyl group in the inside.
  • R 3 and “R 4 ” mean a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. “R 3 ” and “R 4 ” are different from each other. “E 3 ” and “E 4 ” mean an alkylene group having 1 to 8 carbon atoms, and “E 3 ” and “E 4 ” may be different from each other. “C” and “d” mean positive numbers in the range of 1 to 20, preferably 2 to 6. “c” and “d” may be different from each other. 3 ”and“ R 4 ”are both alkyl groups having 10 or more carbon atoms, preferably 10 to 18 carbon atoms.
  • one type of surfactant may be used alone, or two or more types of surfactants may be mixed and used. Further, the surfactant may be attached to only one layer on the surface of the strontium carbonate particles, or two or more layers may be attached. When two or more surfactants are attached, the same type of surfactant may be used for each layer, or different types of surfactants may be used for each layer. Whether the surfactant is attached to the surface of the strontium carbonate particles can be confirmed by measuring the infrared absorption spectrum of the particle surface using a Fourier transform infrared spectrometer (FT-IR). it can.
  • FT-IR Fourier transform infrared spectrometer
  • the method for producing alkaline earth metal compound particles comprises a step of preparing a dispersion (first dispersion) in which an alkaline earth metal compound is dispersed in an aqueous solvent, and a particle dispersibility in the solvent. Dispersion by bringing the primary particles and the surfactant into contact with each other while dispersing the primary particles of the alkaline earth metal compound in the aqueous solvent by applying shear force in the presence of a surfactant for improvement. A dispersion step of obtaining a liquid (second dispersion), and a drying step of drying the second dispersion at a temperature of 100 to 300 ° C. to form a powder.
  • the method for producing the alkaline earth metal compound particles before the surface treatment is not particularly limited, but there may be mentioned a method of reacting the alkaline earth metal compound as a raw material to produce an aqueous slurry and aging it. it can.
  • aqueous slurry By introducing carbon dioxide gas in the presence of a crystal growth inhibitor such as tartaric acid while stirring an aqueous solution or aqueous suspension (hereinafter, aqueous slurry) of strontium hydroxide as a raw material, strontium hydroxide is carbonated. Make it. Thereby, substantially spherical strontium carbonate particles having a small aspect ratio are generated.
  • the method of manufacturing substantially spherical strontium carbonate particles may be as described in International Publication No. 2011/052680.
  • the substantially spherical strontium carbonate particles can be grown to acicular strontium carbonate particles by aging them at a predetermined temperature and time.
  • a surfactant may be imparted to the strontium carbonate particles.
  • a surfactant is added to the aqueous slurry while applying a shearing force to the aqueous slurry after aging with a known stirring device such as a stirring blade mixer.
  • a stirring device such as a stirring blade mixer.
  • the aqueous slurry obtained by the above method can be heat-dried by a drying method using a thermal dryer such as a spray dryer to obtain a dried product of highly dispersible strontium carbonate particles.
  • the highly dispersible alkaline earth metal compound particles according to one embodiment are excellent in dispersibility when dispersed in a solvent, they can be used in various applications.
  • the aqueous resin dispersion according to one embodiment is not particularly limited, but preferably includes an aqueous resin made of a polyurethane resin.
  • the composition of the polyurethane resin is not particularly limited.
  • the polyurethane resin is preferably obtained from at least one of polyester polyol, polyether polyol, and polycarbonate polyol, for example.
  • the polyurethane resin is obtained from at least a polycarbonate polyol.
  • the polyurethane resin is obtained from a polyol compound (a) containing at least a polycarbonate polyol, an acidic group-containing polyol (b), and a polyisocyanate (c).
  • the polyol compound (a) is not particularly limited as long as it contains a polycarbonate polyol.
  • the polycarbonate polyol is a high molecular weight polyol in which polyol monomers such as diol are connected by a carbonate bond, and the number average molecular weight of the polycarbonate polyol is preferably 400 to 8,000.
  • the polycarbonate polyol may be obtained from one or more polyol monomers and a carbonate or phosgene.
  • the polycarbonate polyol is preferably obtained from one or more polyol monomers and a carbonate ester from the viewpoint of easy production and the absence of by-products of terminal chlorinated products.
  • the polycarbonate polyol in this embodiment may contain an ether bond or an ester bond having a number equal to or less than the average number of carbonate bonds in one molecule.
  • the kind of polyol monomer for constituting the polycarbonate polyol is not particularly limited, and examples thereof include an aliphatic polyol monomer, an aliphatic polyol monomer, an alicyclic structure-containing polyol monomer, and an aromatic polyol monomer.
  • Such various polyol monomers are not particularly limited. For example, diols described in International Publication No. 2010-098316 can be used.
  • the carbonate ester is not particularly limited, and examples thereof include aliphatic carbonate esters such as dimethyl carbonate and diethyl carbonate, aromatic carbonate esters such as diphenyl carbonate, and cyclic carbonate esters such as ethylene carbonate.
  • aliphatic carbonate esters such as dimethyl carbonate and diethyl carbonate
  • aromatic carbonate esters such as diphenyl carbonate
  • cyclic carbonate esters such as ethylene carbonate.
  • phosgene or the like capable of producing a polycarbonate polyol can be used.
  • the carbonate ester is preferably an aliphatic carbonate ester, particularly preferably dimethyl carbonate, from the viewpoint of ease of production of the polycarbonate polyol.
  • the polyol compound (a) is not particularly limited as long as it contains a polycarbonate polyol, and may contain other polyols.
  • Other polyols are not particularly limited as long as they are different from the polycarbonate polyols described above, and examples thereof include polyether polyols and polyester polyols such as diols having a number average molecular weight of less than 400.
  • the acidic group containing polyol (b) mentioned later is not included.
  • a polyol compound (a) may be used individually by 1 type, and may be used in combination of multiple types.
  • the acidic group-containing polyol (b) contains two or more hydroxyl groups and one or more acidic groups in one molecule.
  • the acidic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group.
  • the acidic group-containing polyol (b) specifically, those described in International Publication No. 2010-098316 can be used.
  • the acidic group-containing polyol (b) may be used alone or in combination of two or more.
  • polyisocyanate compound (c) For example, aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate etc. are mentioned. It is preferable to use an alicyclic polyisocyanate as the polyisocyanate compound (c) because of the advantage that a coating film that hardly yellows is obtained.
  • specific examples of the various polyisocyanates include compounds described in International Publication No. 2010-098316.
  • the polyisocyanate compound (c) a diisocyanate compound having two isocyanato groups per molecule can be suitably used. These polyisocyanate compounds may be used individually by 1 type, and may be used in combination of multiple types.
  • the polyurethane resin is preferably obtained from a urethane prepolymer obtained from the above-described polyol compound (a), acidic group-containing polyol (b), and polyisocyanate compound (c).
  • urethane prepolymers may be produced from various production methods. Examples of the method for producing the urethane prepolymer include a method in which a mixture of the polyol compound (a) and the acidic group-containing polyol (b) is reacted with the polyisocyanate compound (c).
  • a urethanization catalyst may be used.
  • a urethanization catalyst for example, a catalyst described in International Publication No. 2010-098316 can be used.
  • the reaction performed using the polyol compound (a), the acidic group-containing polyol (b), and the polyisocyanate compound (c) as constituent components may be performed in the absence of a solvent or in the presence of an organic solvent.
  • the organic solvent include acetone, ethyl methyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl acetate.
  • the method for producing the aqueous resin dispersion in the present embodiment is appropriately selected according to the target aqueous resin dispersion and is not particularly limited.
  • a production method there is a method in which all raw materials are mixed, reacted, and dispersed in an aqueous medium to obtain an aqueous resin dispersion.
  • the acidic group of the urethane prepolymer is added inside.
  • the aqueous resin dispersion can be obtained by adding and dispersing the polyurethane prepolymer in an aqueous medium and optionally reacting with a chain extender.
  • a compound having reactivity with an isocyanate group of a urethane prepolymer may be used as a chain extender.
  • a compound having reactivity with an isocyanate group of a urethane prepolymer for example, those described in International Publication No. 2010-004951 can be used.
  • Such compounds may be used alone or in combination of two or more.
  • a polyurethane resin that is an aqueous resin is dispersed in an aqueous medium.
  • the aqueous medium include water and a mixed medium of water and a hydrophilic organic solvent.
  • water include clean water, ion exchange water, distilled water, and ultrapure water. In consideration of easy availability and prevention of particle instability due to the influence of salt, it is preferable to use ion-exchanged water as the aqueous medium.
  • hydrophilic organic solvent examples include lower monohydric alcohols such as methanol, ethanol and propanol; polyhydric alcohols such as ethylene glycol and glycerin; N-methylmorpholine, dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone and the like.
  • examples include aprotic hydrophilic organic solvents.
  • the amount of the hydrophilic organic solvent in the aqueous medium is preferably 0 to 20% by weight.
  • the aqueous resin dispersion composition is different from the aqueous resin dispersion as long as the effects of the present invention are not impaired, in addition to the alkaline earth metal compound particles and the aqueous resin dispersion, depending on the purpose and application. Resins, curing agents, additives and the like may be included.
  • the aforementioned aqueous resin may be an active energy ray curable resin or a thermosetting resin.
  • active energy rays include particle beams such as electron beams, and electromagnetic waves such as X-rays and ultraviolet rays. From the viewpoint of ease of handling and manufacturing cost, the resin is preferably an ultraviolet curable resin.
  • the resin itself may have curability, but the resin composition may contain a component that cures the resin.
  • the resin composition may appropriately include, for example, a photo-radical polymerizable component, a photo-ion polymerizable component, or the like as a component that imparts ultraviolet curability, depending on the purpose.
  • components that impart ultraviolet curability include acrylic monomers and acrylic oligomers. Specific examples include a polyfunctional oligomer having a (meth) acryloyl group, a polyfunctional monomer having three or more (meth) acryloyl groups in a molecule, and a monofunctional or bifunctional monomer having a (meth) acryloyl group. .
  • polyfunctional oligomer having a (meth) acryloyl group examples include polyester (meth) acrylate, polyurethane (meth) acrylate, and epoxy (meth) acrylate.
  • polyfunctional monomers having three or more (meth) acryloyl groups in one molecule include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, tris ( (Meth) acryloyloxyethyl) isocyanurate, tris ((meth) acryloyloxypropyl) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipenta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra
  • Examples of mono- or bifunctional monomers having a (meth) acryloyl group include cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, di Cyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl ( Monofunctional (meth) acrylate monomers such as (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate; ethylene glycol di (meth
  • the resin composition may further contain additives such as thickeners, photosensitizers, curing catalysts, ultraviolet absorbers, light stabilizers, antifoaming agents, plasticizers, surface conditioners, anti-settling agents, as necessary. May be included.
  • additives such as thickeners, photosensitizers, curing catalysts, ultraviolet absorbers, light stabilizers, antifoaming agents, plasticizers, surface conditioners, anti-settling agents, as necessary. May be included.
  • One type of additive may be used alone, or a plurality of types of additives may be used in combination. In addition, these additives can be used in the amount of the range generally used.
  • the solid content thereof is preferably 1 to 70% by weight, and more preferably 5 to 50% by weight of the entire aqueous resin dispersion.
  • the solid content of the aqueous resin dispersion is a component remaining as a coating film after the aqueous resin dispersion is applied to a substrate, dried, and crosslinked by light irradiation or / and heating. Therefore, the aqueous medium and the neutralizing agent are not included in the solid content.
  • Aqueous resin containing alkaline earth metal compound particles by dispersing alkaline earth metal compound particles in a solvent such as water, adding an aqueous resin dispersion composition in the solvent, and stirring for a predetermined time
  • a coating liquid comprising the dispersion composition can be produced.
  • a coating film of an aqueous resin composition containing alkaline earth metal compound particles can be formed on a transparent substrate by applying the coating solution on the transparent substrate and drying the coating solution to remove the solvent. .
  • the coating liquid may be applied by any method.
  • the coating method include a T-die method, a doctor blade method, a bar coater method, a roll coater method, and a lip coater method.
  • the inventor of the present application has obtained a novel aqueous resin dispersion composition imparted with functionality by incorporating alkaline earth metal compound particles such as strontium carbonate into the aqueous resin dispersion composition, and thereby obtained. It was found that a coating film can be provided. It should be noted that the composition of the coating film is the same as the composition of the solid content of the aqueous resin dispersion composition.
  • the inventors of the present application have found that the adhesiveness of the coating film can be improved by adding alkaline earth metal compound particles to the aqueous resin. Moreover, since the dispersibility of the alkaline earth metal compound particles in the aqueous resin dispersion composition is high, the transparency and haze of the coating film containing the aqueous resin composition can be maintained.
  • the average major axis of the alkaline earth metal carbonate particles is 500 nm or less, preferably 10 to 100 nm, more preferably 15 to 75 nm, and still more preferably 20 to 50 nm.
  • the average major axis is less than 10 nm, the particles are too small to easily aggregate and the dispersibility tends to decrease.
  • the average major axis exceeds 500 nm, the particles are too large and the transparency tends to decrease when mixed with the resin.
  • the above surfactant is applied to the surface of the alkaline earth metal compound particles.
  • the alkaline earth metal compound particles have high dispersibility in the aqueous resin dispersion. Thereby, transparency or haze of a coating film can be maintained.
  • the adhesiveness of a coating film can be improved more by disperse
  • the type of the water-based resin is as described above, and is preferably a polyurethane resin.
  • the aqueous polyurethane resin is excellent in light resistance / weather resistance / heat resistance. Therefore, it is suitable as a coating film for an optical film.
  • the average aspect ratio of the alkaline earth metal carbonate fine particles is not particularly limited, but is usually in the range of 1.0 to 5.0, preferably 2.0 to 4.5, more preferably 2.5 to 4.0. It is. When the average aspect ratio exceeds 5.0, the fine particles become too long and easily broken, and the particle size distribution tends to be lowered. If the aspect ratio is too small, it may be difficult to exert an effect on birefringence control as an optical film.
  • the coating film obtained from the above aqueous resin dispersion composition can be suitably used as an optical film. Since the optical film contains fine and highly dispersed alkaline earth metal carbonate fine powder, it is excellent in transparency, and the content of the alkaline earth metal carbonate powder in the entire optical film should be adjusted. Thus, the birefringence of the optical film can be adjusted.
  • polyurethane resin exhibits positive intrinsic birefringence
  • an optical film having negative birefringence can be obtained by adding alkaline earth metal carbonate particles to polyurethane resin.
  • Example 1 (Example of production of aqueous resin dispersion) Polycarbonate diol obtained by reacting 1,4-cyclohexanedimethanol and carbonate ester with polyol component (ETERRNACOLL (registered trademark) UC100; manufactured by Ube Industries; number average molecular weight 1030) in a reaction apparatus equipped with a stirrer and a heater ) 160 g, 18.7 g of polytetramethylene ether glycol (PTMG) having a number average molecular weight of 2030, 22.1 g of 2,2-dimethylolpropionic acid, and 147 g of hydrogenated MDI are mixed with N-methyl-2-pyrrolidone (NMP).
  • ETERRNACOLL registered trademark
  • UC100 polyol component
  • NMP N-methyl-2-pyrrolidone
  • aqueous slurry of 300 g of strontium carbonate particles having an average major axis of 35 nm and an average aspect ratio of 2.1 having a concentration of 5% by mass is placed in a 300 mL beaker, and a polycarboxylic acid copolymer type surfactant (hereinafter referred to as “surfactant 1”).
  • surfactant 1 a polycarboxylic acid copolymer type surfactant
  • the weight of the strontium carbonate particles in the solid content in the aqueous resin dispersion composition was 10% by mass. That is, the weight of strontium carbonate particles in the polyurethane film described later is 10% by mass.
  • PET polyethylene terephthalate
  • Example 2 Among the methods for preparing the SrCO 3 -added dope solution, the above method was used except that 0.3 g of strontium carbonate particles (powder) obtained by drying the dispersion used in Example 1 was added instead of the strontium carbonate particle dispersion. The same.
  • the obtained polyurethane film is designated as B.
  • the visible light transmittance of the polyurethane film B was measured. The results are shown in Table 1.
  • the weight of the strontium carbonate particles in the solid content in the aqueous resin dispersion composition was 10% by mass. That is, the weight of the strontium carbonate particles in the aforementioned polyurethane film is 10% by mass.
  • the strontium carbonate particle-containing aqueous polyurethane resin dispersion composition has the functions of the strontium carbonate particles, such as radio wave absorption performance, radiation control, optical property control, etc. Casing, home appliance housings, personal computer housings, decorative films, optical films (optical resin materials), synthetic resin moldings such as flooring materials (paint compositions) and coating agents (coating agents)
  • the composition can be used for various applications such as radiation shielding materials.
  • Example 3 Example of production of aqueous resin dispersion
  • Polycarbonate diol obtained by reacting 1,4-cyclohexanedimethanol and carbonate ester with polyol component (ETERRNACOLL (registered trademark) UC100; manufactured by Ube Industries; number average molecular weight 1030) in a reaction apparatus equipped with a stirrer and a heater 160 g), polytetramethylene ether glycol (number average molecular weight 2030, 18.7 g), 2,2-dimethylolpropionic acid (22.1 g), hydrogenated MDI (147 g), and N-ethyl- In 2-pyrrolidone (146 g), the mixture was heated at 80 to 90 ° C.
  • ETERRNACOLL registered trademark
  • UC100 polyol component
  • aqueous slurry having a concentration of strontium carbonate particles of 10% by mass is placed in a 300 mL beaker, and 35% by mass of a carboxylic acid anionic surfactant (hereinafter referred to as “surfactant 2”) is added to the solid content.
  • surfactant 2 a carboxylic acid anionic surfactant
  • the weight of the strontium carbonate particles in the solid content in the aqueous resin dispersion composition was 10% by mass. That is, the weight of strontium carbonate particles in the polyurethane film described later is 10% by mass.
  • a SrCO 3 -added dope solution is applied to a polyethylene terephthalate (PET) substrate with a wet thickness of 40 ⁇ m. Immediately after the application of the SrCO 3 -added dope solution, it is dried at 60 ° C. for 90 minutes. Then, it left still overnight at room temperature. As a result, a polyurethane film was formed on the PET substrate.
  • PET polyethylene terephthalate
  • Adhesion test method The adhesion of the polyurethane film (polyurethane resin composition) to the PET substrate was tested by a 100-mass test using a cross cut test / cross cut (JIS K5600) method. The number of polyurethane film pieces remaining on the PET substrate was measured by cutting (dividing) the polyurethane film on the PET substrate into 100 squares, adhering the cellophane tape, and peeling the cellophane tee. Here, one square has a size of 2 mm ⁇ 2 mm.
  • Example 4 The same as Example 3 except that the weight of the strontium carbonate particles in the solid content of the aqueous resin dispersion composition, that is, the weight of the strontium carbonate particles in the polyurethane film was 20% by mass.
  • Example 5 The same as Example 3, except that the weight of the polyurethane resin composition relative to the SrCO 3 added dope was 20 mass%.
  • Example 6 Example 3 except that the surfactant imparted to the strontium carbonate particles was changed to a phosphoric acid anionic surfactant (hereinafter referred to as “surfactant 3”), and 30% by mass was added to the solid content. It is the same.
  • surfactant 3 a phosphoric acid anionic surfactant
  • Example 7 The same as Example 5 except that the surfactant applied to the strontium carbonate particles was changed to the surfactant 3.
  • Example 1 The same as Example 3 except that the strontium carbonate particles were not added to the aqueous resin dispersion.
  • Example 2 The same as Example 5 except that no strontium carbonate particles were added to the aqueous resin dispersion.
  • Example 8 Example of production of UV curable aqueous resin dispersion
  • ETERNACOLL registered trademark
  • UM90 3: 1 polycarbonate diol obtained by reacting a polyol mixture with carbonate ester, 125 g), 2,2-dimethylolpropionic acid (22.4 g), and isophorone diisocyanate (120 g) was heated in N-ethylpyrrolidone (100 g) in the presence of dibutyltin dilaurate (0.2 g) at 80-90 ° C.
  • a strontium carbonate particle dispersion was obtained in the same manner as in Example 1 except that the water slurry had a concentration of strontium carbonate particles of 10% by mass.
  • the weight of the strontium carbonate particles in the solid content in the aqueous resin dispersion composition was 10% by mass. That is, the weight of strontium carbonate in the polyurethane film described later is 10% by mass.
  • PET film forming method Polyurethane film forming method
  • the SrCO 3 -added dope solution was applied onto a polyethylene terephthalate (hereinafter “PET”) film and dried at 60 ° C. for 3 hours.
  • the coating film was peeled off from the PET substrate and further dried at 60 ° C. for 2 hours to obtain a polyurethane film.
  • the out-of-plane retardation (thickness direction retardation; thickness direction retardation) Rth of the polyurethane film was measured using a phase measuring device (KOBRA-WR manufactured by Oji Scientific Instruments).
  • the phase measuring device described above includes an in-plane retardation (retardation) R0 measured by light perpendicularly incident on a measurement object (polyurethane film) and a phase difference measured by light incident on the measurement object at an incident angle ⁇ (
  • the out-of-plane retardation Rth is calculated from the retardation R ⁇ , the thickness d (input value) of the measurement object, and the average refractive index N avr (input value) of the measurement object.
  • the incident angle ⁇ is 40 °, and the wavelength of light is 547.4 nm.
  • Nx, Ny, and Nz mean the refractive indexes of the measurement object in the X-axis direction, the Y-axis direction, and the Z-axis direction, respectively.
  • the X-axis direction is the direction of the slow axis.
  • the Y-axis direction is the direction of the fast axis.
  • the Z-axis direction is the thickness direction of the measurement object.
  • the average refractive index of the polyurethane film was assumed to be 1.5050.
  • d means the thickness of the measurement object.
  • An out-of-plane birefringence value ⁇ P was calculated from the measured out-of-plane phase difference Rth.
  • the thickness d of the measurement object can be measured with a micrometer.
  • Example 9 is the same as Example 8 except that the polyurethane film of Example 8 was irradiated with ultraviolet light having an integrated light amount of 1000 mJ / cm 2 after drying.
  • Example 10 (Method for producing SrCO 3 -added dope solution) The same as Example 9, except that 120 g of the dispersion and 0.3 g of leveling agent BYK-345 (BYK) were added to 100 g of the aqueous resin dispersion obtained in the above production example.
  • BYK leveling agent BYK-345
  • the weight of the strontium carbonate particles in the solid content in the aqueous resin dispersion composition was 20% by mass. That is, the weight of the strontium carbonate particles in the polyurethane film is 20% by mass.
  • Example 9 is the same as Example 9 except that the polyurethane film of Example 10 was irradiated with ultraviolet light having an integrated light quantity of 1000 mJ / cm 2 after drying.
  • Example 3 A film was obtained in the same manner as in Example 8 except that strontium carbonate particles were not added.
  • Example 4 A film was obtained in the same manner as in Example 9 except that strontium carbonate particles were not added.
  • FIG. 1 is a graph showing the relationship between the out-of-plane birefringence value ⁇ P and the amount of strontium carbonate particles added.
  • in-plane birefringence ⁇ Nxy ⁇ 0 when the solid content of the aqueous resin dispersion composition, that is, the concentration of strontium carbonate particles with respect to the entire optical film is about 10% by weight.
  • in-plane birefringence ⁇ Nxy ⁇ 0 at this time, and a positive C plate optical film can be provided.
  • a positive A plate and a positive C plate is used as a retardation plate in order to increase the contrast in an oblique direction in a liquid crystal display device such as an IPS mode. Can be provided.
  • an optical film having a positive C plate is required in the design depending on the application.
  • the haze of the optical film is maintained at less than 3%, and the visible light transmittance is maintained at 90% or more.
  • an optical film with high transparency can be provided while controlling the birefringence value.
  • the present inventor has found that the haze of the optical film after UV curing is lower than the haze of the optical film before UV curing.
  • the solid content of the aqueous resin dispersion composition that is, the strontium carbonate particles relative to the entire optical film. It can be seen that when the concentration is 2.5% by weight or more, the out-of-plane birefringence ⁇ P of the optical film can be made negative.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une nouvelle composition de résine qui est pourvue de la fonctionnalité de particules de composé de métal alcalino-terreux, telles que des particules de carbonate de strontium. La présente invention concerne une composition aqueuse de dispersion de résine qui contient des particules de composé de métal alcalino-terreux et une dispersion aqueuse de résine.
PCT/JP2016/081923 2015-10-30 2016-10-27 Composition aqueuse de dispersion de résine contenant des particules de composé de métal alcalino-terreux WO2017073684A1 (fr)

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Cited By (1)

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US11548971B2 (en) * 2018-04-26 2023-01-10 Yifeng New Materials Co., Ltd. Method for producing a resin lens from a polyisocyanate and release agent at reduced pressure

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CA3241083A1 (fr) * 2021-12-17 2023-06-22 Keith A. ALDERFER Composition de revetement avec du carbonate de cerium(iii) et un photo-initiateur

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JPH09169925A (ja) * 1995-12-20 1997-06-30 Nittetsu Mining Co Ltd 表面改質重質炭酸カルシウムとその製造方法及び水系塗料組成物
JP2010006896A (ja) * 2008-06-25 2010-01-14 Nitto Denko Corp 水分散型粘着剤組成物、粘着型光学フィルムおよび画像表示装置
JP2014509344A (ja) * 2011-02-23 2014-04-17 オムヤ・インターナツイオナール・アー・ゲー サブミクロンの炭酸カルシウムを含む粒子を含むコーティング組成物、その調製方法及びコーティング組成物におけるサブミクロンの炭酸カルシウムを含む粒子の使用

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JP4140884B2 (ja) * 2002-07-04 2008-08-27 独立行政法人科学技術振興機構 炭酸ストロンチウムの製造方法、非複屈折性光学樹脂材料並びに光学素子
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JP6158020B2 (ja) * 2012-09-28 2017-07-05 宇部マテリアルズ株式会社 針状炭酸ストロンチウム微粉末

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JPH09169925A (ja) * 1995-12-20 1997-06-30 Nittetsu Mining Co Ltd 表面改質重質炭酸カルシウムとその製造方法及び水系塗料組成物
JP2010006896A (ja) * 2008-06-25 2010-01-14 Nitto Denko Corp 水分散型粘着剤組成物、粘着型光学フィルムおよび画像表示装置
JP2014509344A (ja) * 2011-02-23 2014-04-17 オムヤ・インターナツイオナール・アー・ゲー サブミクロンの炭酸カルシウムを含む粒子を含むコーティング組成物、その調製方法及びコーティング組成物におけるサブミクロンの炭酸カルシウムを含む粒子の使用

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11548971B2 (en) * 2018-04-26 2023-01-10 Yifeng New Materials Co., Ltd. Method for producing a resin lens from a polyisocyanate and release agent at reduced pressure

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