WO2023027157A1 - 赤外線硬化型インク組成物、赤外線硬化物、赤外線硬化物の製造方法 - Google Patents

赤外線硬化型インク組成物、赤外線硬化物、赤外線硬化物の製造方法 Download PDF

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WO2023027157A1
WO2023027157A1 PCT/JP2022/032099 JP2022032099W WO2023027157A1 WO 2023027157 A1 WO2023027157 A1 WO 2023027157A1 JP 2022032099 W JP2022032099 W JP 2022032099W WO 2023027157 A1 WO2023027157 A1 WO 2023027157A1
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Prior art keywords
infrared
ink composition
curable ink
absorbing particles
particles
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English (en)
French (fr)
Japanese (ja)
Inventor
昭也 野下
武 長南
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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Priority to JP2023543988A priority Critical patent/JP7823666B2/ja
Priority to US18/684,019 priority patent/US20250136832A1/en
Priority to KR1020247007249A priority patent/KR20240051951A/ko
Priority to EP22861445.9A priority patent/EP4393882A4/en
Priority to CN202280057252.0A priority patent/CN117836377A/zh
Publication of WO2023027157A1 publication Critical patent/WO2023027157A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention relates to an infrared curable ink composition, an infrared curable product, and a method for producing an infrared curable product.
  • UV curable paints that are cured using ultraviolet light are widely known as environmentally friendly paints that are excellent in reducing CO 2 because they can be printed without heating (Patent Document 1).
  • an ultraviolet curable ink or paint when a composition that undergoes radical polymerization upon irradiation with ultraviolet rays is used as an ultraviolet curable ink or paint, the presence of oxygen inhibits polymerization (curing). Moreover, when a composition that undergoes cationic polymerization by irradiation with ultraviolet rays is used, there is a problem that a strong acid is generated during the polymerization. Furthermore, in order to improve the light resistance of the printed surface or the coated surface formed by applying ultraviolet curable ink or paint, an ultraviolet absorber is generally used. When the agent is used, there is a problem that curing by ultraviolet irradiation is inhibited.
  • Patent Documents 2 and 3 propose an infrared curable composition that is cured by irradiation of infrared light instead of ultraviolet light.
  • Patent Document 2 discloses a technique using an organic infrared absorber such as a cyanine dye
  • Patent Document 3 discloses a technique using a phosphonic acid copper salt as an infrared absorber.
  • Patent Documents 2 and 3 all have the problem of insufficient infrared absorption characteristics, and an infrared curable composition with excellent infrared absorption characteristics has been desired.
  • infrared curable compositions have been required to have excellent long-term storage stability in order to be applied to various uses.
  • An object of one aspect of the present invention is to provide an infrared curable ink composition that has excellent infrared absorption properties and long-term storage stability.
  • the infrared absorbing particles have the general formula M x W y O z (M elements are H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, one or more elements selected from Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.001 ⁇ x/y ⁇ 1, Provided is an infrared curable ink composition containing composite tungsten oxide particles represented by 3.0 ⁇ z/y).
  • M elements are H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni
  • One aspect of the present invention can provide an infrared curable ink composition that has excellent infrared absorption properties and long-term storage stability.
  • FIG. 1 is an explanatory diagram of a hybrid plasma reactor in which DC plasma and high-frequency plasma are superimposed.
  • FIG. 2 is an explanatory diagram of a high-frequency plasma reactor.
  • FIG. 3 is a diagram schematically showing an infrared curable ink composition according to this embodiment.
  • the infrared curable ink composition (hereinafter also referred to as "ink composition") of the present embodiment can contain infrared absorbing particles and a thermosetting resin.
  • the infrared curable ink composition of the present embodiment can be composed only of infrared absorbing particles and a thermosetting resin, but even in this case, the inclusion of unavoidable impurities is not excluded.
  • the infrared absorbing particles have the general formula M x W y O z
  • M elements are H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh , Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te , Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, and 0.001 ⁇ x/y ⁇ 1 , 3.0 ⁇ z/y).
  • the inventors of the present invention have investigated an infrared curable ink composition that has excellent infrared absorption properties and long-term storage stability. As a result, it was found that an infrared curable ink composition containing composite tungsten oxide particles having a predetermined composition as infrared absorbing particles has excellent infrared absorbing characteristics because the composite tungsten oxide has excellent infrared absorbing characteristics. , completed the present invention. According to such an infrared curable ink composition, the thermosetting resin can be efficiently cured by utilizing the heat generated when the infrared absorbing particles absorb infrared rays, particularly near infrared rays.
  • the infrared curable ink composition in which the infrared absorbing particles contain composite tungsten oxide particles having a predetermined composition, transparency and long-term storage stability are also excellent.
  • infrared absorbing particles that can be suitably used in the infrared curable ink composition of the present embodiment and a method for producing the infrared absorbing particles will be described.
  • Infrared absorbing particles (1) Composition, crystal structure
  • the inventors of the present invention include composite tungsten oxide particles, carbon black powder, and tin-added indium oxide (ITO). I examined the powder.
  • the infrared curable ink composition of the present embodiment can contain composite tungsten oxide particles represented by the general formula M x W y O z as infrared absorbing particles.
  • the M element in the above general formula includes H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, It is one or more elements selected from Ta, Re, Be, Hf, Os, Bi, and I. W is tungsten and O is oxygen. x, y and z can satisfy 0.001 ⁇ x/y ⁇ 1 and 3.0 ⁇ z/y.
  • materials containing free electrons are known to exhibit a reflection absorption response due to plasma oscillation to electromagnetic waves with a wavelength of 200 nm to 2600 nm, which is around the range of sunlight.
  • the powder of the material containing free electrons is particles smaller than the wavelength of light, geometric scattering in the visible light region (wavelength of 380 nm or more and 780 nm or less) is reduced, and transparency in the visible light region is obtained. It has been known.
  • the term “transparency” is used to mean that light in the visible region is less scattered and highly transmissive.
  • Tungsten oxides represented by the general formula WO 3-a and so-called tungsten bronzes obtained by adding a positive element such as Na to tungsten trioxide are conductive materials and are known to contain free electrons. there is Analysis of single crystals of these materials suggests that free electrons respond to light in the near-infrared region.
  • tungsten trioxide does not have effective free electrons, so it has little absorption and reflection characteristics in the infrared region, and is not effective as an infrared absorbing material.
  • free electrons are generated in the tungsten oxide by reducing the ratio of oxygen to tungsten in tungsten trioxide to less than 3.
  • the inventors of the present invention conducted further research on tungsten oxides and composite tungsten oxides in order to obtain infrared absorbing particles with excellent long-term storage stability.
  • the infrared absorbing particles containing composite tungsten oxide particles represented by the general formula M x W y O z by setting 3.0 ⁇ z/y for y and z in the general formula, It was found that both infrared absorption characteristics and long-term storage stability can be achieved.
  • the long-term storage stability means that the infrared absorbing particles, etc., have excellent infrared absorbing properties even when placed in a room temperature environment for a long period of time, for example, 3 months. It means that it can absorb the heat and supply the amount of heat to cure the thermosetting resin.
  • the infrared absorbing particles used in the ink composition of the present embodiment can contain composite tungsten oxide particles represented by the general formula M x W y O z as described above.
  • the infrared absorbing particles can also be composed of composite tungsten oxide particles represented by the above general formula. However, even in this case, it does not exclude the inclusion of unavoidable components mixed in the manufacturing process or the like.
  • the M element in the above general formula is, as described above, H, He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru , Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se , Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I are preferable.
  • the M element more preferably belongs to alkali metals, alkaline earth metal elements, transition metal elements, Group 4B elements, and Group 5B elements. .
  • the composite tungsten oxide When the composite tungsten oxide contains crystals having a hexagonal crystal structure, the transmittance of the particles in the visible light region is particularly improved, and the absorption in the near-infrared region is particularly improved. Therefore, the composite tungsten oxide preferably has a hexagonal crystal structure.
  • the hexagonal crystal structure six octahedrons formed by WO 6 units are aggregated to form a hexagonal void (tunnel), and an M element is arranged in the void to form one unit. , and is composed of a large number of this one unit.
  • the composite tungsten oxide is not limited to containing a crystal having a hexagonal crystal structure. is configured, and the M element is arranged in the gap, the transmittance in the visible light region can be particularly improved, and the absorption in the near infrared region can be particularly improved. Therefore, even if the composite tungsten oxide does not contain a crystal having a hexagonal crystal structure and only has the unit structure, a high effect can be obtained.
  • the composite tungsten oxide has a structure in which cations of the M element are added to the hexagonal voids, absorption in the near-infrared region is particularly improved.
  • the M element having a large ion radius is added, the hexagonal crystal structure and the structure described above are likely to be formed.
  • the M element preferably contains one or more elements selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn. More preferably, it is one or more elements selected from Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn.
  • composite tungsten oxide particles containing one or more types selected from Cs and Rb among these M elements with large ionic radii hexagonal crystals and the above structures are easily formed, and absorption in the near-infrared region and transmission in the visible light region, and exhibit particularly high performance.
  • x/y which indicates the content ratio of element M to 1 mol of tungsten in the general formula described above, is 0.2 or more and 0. 0.5 or less is preferable, and 0.33 is more preferable. It is considered that the element M is arranged in all the hexagonal voids because the value of x/y is 0.33.
  • the composite tungsten oxide contains crystals other than the above-mentioned hexagonal crystals, such as tetragonal crystals and cubic crystals, it is also effective as an infrared absorbing material.
  • each of the cubic and tetragonal composite tungsten oxides has a suitable range and an upper limit for the amount of the element M to be added, which is derived from the structure.
  • the upper limit is 1 mol for a cubic system and about 0.5 mol for a tetragonal system.
  • the upper limit of x/y which is the content ratio of the M element to 1 mol of tungsten, varies depending on the type of the M element, but in the case of a tetragonal crystal, industrial production is easy at about 0.5 mol. be.
  • the absorption position in the near-infrared region tends to change, and the absorption position in the near-infrared region moves to the longer wavelength side in the tetragonal crystal than in the cubic crystal.
  • hexagonal crystals tend to shift to longer wavelengths than tetragonal crystals.
  • absorption in the visible light region is lowest in hexagonal crystals, next in tetragonal crystals, and highest in cubic crystals. Therefore, it is preferable to select the crystal system to be contained according to the required performance and the like.
  • the composite tungsten oxide particles when used in an application that requires transmission of light in the visible region and absorption of light in the near-infrared region, the composite tungsten oxide particles preferably contain hexagonal crystals.
  • the infrared curable ink composition may contain pigments and dyes as described later. It preferably absorbs light.
  • the composite tungsten oxide By combining the control of the oxygen content and the addition of the element M that generates free electrons to the composite tungsten oxide, it is possible to obtain an infrared absorbing material that is more efficient and has excellent long-term storage stability.
  • M x W y O z When the general formula of the composite tungsten oxide, which is an infrared absorbing material that uses both the control of the oxygen content and the addition of an element that generates free electrons, is described as M x W y O z , x and y are 0. .001 ⁇ x/y ⁇ 1, preferably 0.20 ⁇ x/y ⁇ 0.37.
  • y and z in the above general formula preferably satisfy the relationship of 3.0 ⁇ z/y, preferably 3.0 ⁇ z/y ⁇ 3.4, and 3.0 ⁇ z/y ⁇ 3. 3 is more preferably satisfied, and 3.0 ⁇ z/y ⁇ 3.22 is even more preferable.
  • the composite tungsten oxide contained in the infrared-absorbing particles according to the present embodiment has z/y exceeding 3.
  • the crystal structure of the crystals contained in the composite tungsten oxide particles contained in the infrared absorbing particles according to the present embodiment can be confirmed by an X-ray diffraction pattern by a powder X-ray diffraction method ( ⁇ -2 ⁇ method).
  • the infrared absorbing particles of the present embodiment have a maximum value in the wavelength range of 350 nm or more and 600 nm or less, and exhibit light transmission characteristics having a minimum value in the wavelength range of 800 nm or more and 2100 nm or less. It can be preserved. It is more preferable that the infrared absorbing particles of the present embodiment exhibit light transmission characteristics having a maximum value in the wavelength range of 440 nm or more and 600 nm or less and a minimum value in the wavelength range of 1150 nm or more and 2100 nm or less.
  • Lattice constant Let the general formula of the composite tungsten oxide contained in the composite tungsten oxide particles be M x W y O z as described above.
  • the lattice constant of the composite tungsten oxide is 7.3850 ⁇ or more on the a-axis. It is preferably 7.4186 ⁇ or less, and the c-axis is preferably 7.5600 ⁇ or more and 7.6240 ⁇ or less.
  • the lattice constant of the composite tungsten oxide is more preferably composed of one or more elements selected from Cs and Rb.
  • the lattice constant can be calculated using the Rietveld method.
  • the infrared absorbing particles according to the present embodiment preferably have a particle size of 100 nm or less.
  • the particle diameter is more preferably 10 nm or more and 100 nm or less, more preferably 10 nm or more and 80 nm or less, particularly preferably 10 nm or more and 60 nm or less, and most preferably 10 nm or more and 40 nm or less.
  • the particle size of the infrared absorbing particles is in the range of 10 nm or more and 40 nm or less, the most excellent near infrared absorbing properties are exhibited.
  • the particle size is the size of individual infrared absorbing particles that are not agglomerated, that is, the particle size of individual particles.
  • the particle size here does not include the size of aggregates of infrared absorbing particles, and is different from the dispersed particle size.
  • the particle size here can be calculated by measuring the particle size of a plurality of particles using a transmission electron microscope (TEM) or the like while the infrared absorbing particles are dispersed.
  • TEM transmission electron microscope
  • the diameter of the smallest circle circumscribing the particles can be taken as the particle diameter of the particles.
  • the particle diameters of a plurality of particles are measured for each particle using a transmission electron microscope as described above, it is preferable that the particle diameters of all the particles satisfy the above range.
  • the number of particles to be measured is not particularly limited, it is preferably 10 or more and 50 or less, for example.
  • the crystallite size of the composite tungsten oxide is preferably 10 nm or more and 100 nm or less, more preferably 10 nm or more and 80 nm or less. It is more preferably 10 nm or more and 60 nm or less, and particularly preferably 10 nm or more and 40 nm or less. This is because when the crystallite diameter is in the range of 10 nm or more and 40 nm or less, particularly excellent near-infrared absorption characteristics are exhibited.
  • the crystallite size of the composite tungsten oxide particles contained in the infrared absorbing particles can be calculated using the Rietveld method from the X-ray diffraction pattern measured by the powder X-ray diffraction method ( ⁇ -2 ⁇ method).
  • Dispersed particle size the infrared cured product, which is the infrared absorbing particle dispersion containing the composite tungsten oxide particles according to the present embodiment, absorbs light in the near infrared region, especially near a wavelength of 1000 nm. Many of them have a transmission color tone of blue to green.
  • the dispersed particle size of the infrared absorbing particles of the present embodiment can be selected depending on the purpose of use.
  • the infrared absorbing particles when used for applications that maintain transparency, preferably have a dispersed particle size of 800 nm or less. This is because particles with a dispersed particle diameter of 800 nm or less do not completely block light due to scattering, and can maintain visibility in the visible light region and at the same time efficiently maintain transparency.
  • the dispersed particle diameter includes the diameter of aggregates of infrared absorbing particles, and is different from the particle diameter described above.
  • the dispersed particle diameter of the infrared absorbing particles of the present embodiment is preferably 200 nm or less, more preferably 1 nm or more and 200 nm or less, and even more preferably 1 nm or more and 100 nm or less.
  • This is a dispersion containing the infrared-absorbing particles of the present embodiment, as a result of reducing the scattering of light in the visible light region with a wavelength of 380 nm or more and 780 nm or less due to geometric scattering or Mie scattering if the dispersed particle diameter is small. This is because it is possible to prevent the infrared cured product from becoming like frosted glass and failing to obtain clear transparency.
  • the dispersed particle diameter is 200 nm or less
  • the geometric scattering or Mie scattering is reduced, resulting in a Rayleigh scattering region.
  • the scattered light is proportional to the sixth power of the diameter of the dispersed particles, so that as the diameter of the dispersed particles decreases, the scattering decreases and the transparency improves.
  • the dispersed particle size is 100 nm or less, the scattered light is extremely small, which is preferable.
  • the dispersed particle diameter is small, but from the viewpoint of industrial productivity, the infrared absorbing particles preferably have a dispersed particle diameter of 1 nm or more, and is 10 nm or more. is more preferable.
  • the haze (haze value) of the infrared cured product which is an infrared absorbing particle dispersion in which the infrared absorbing particles are dispersed in the medium, is 10% at a visible light transmittance of 85% or less.
  • the haze can be:
  • the dispersed particle size to 100 nm or less
  • the haze can be reduced to 1% or less.
  • the surfaces of the infrared absorbing particles may be coated with a compound containing one or more elements selected from Si, Ti, Zr and Al. Weather resistance can be particularly improved by coating the surface of the infrared absorbing particles with the above compound.
  • the compounds containing one or more elements selected from Si, Ti, Zr, and Al include hydrolysis products of metal chelate compounds containing Si, Ti, Zr, and Al, and hydrolysis products of metal chelate compounds.
  • a hydrolysis product of a metal cyclic oligomer compound, and a polymer of a hydrolysis product of a metal cyclic oligomer compound can be preferably used.
  • the metal chelate compounds and metal cyclic oligomer compounds are preferably metal alkoxides, metal acetylacetonates, and metal carboxylates, they have one or more selected from ether bonds, ester bonds, alkoxy groups, and acetyl groups. is preferred.
  • the operation of coating the surfaces of the infrared absorbing particles with these compounds is preferably performed before preparing the infrared absorbing particle dispersion, the infrared curable ink composition, and the like.
  • Method for producing infrared absorbing particles A configuration example of a method for producing infrared absorbing particles will be described. According to the method for producing infrared absorbing particles of the present embodiment, the infrared absorbing particles described above can be produced. Therefore, a part of the description of the matters that have already been described will be omitted.
  • the composite tungsten oxide particles represented by the general formula M x W y O z contained in the infrared absorbing particles of the present embodiment can be produced, for example, by the following solid-phase reaction method or plasma method.
  • Solid-phase reaction method When producing composite tungsten oxide particles by a solid-phase reaction method, the following steps can be carried out.
  • a raw material mixture is prepared by mixing a tungsten compound and an M element compound (mixing step). It should be noted that the material amount ratio (molar ratio) of the M element and tungsten in the raw material mixture should be the ratio of x and y in the above general formula of the target composite tungsten oxide particles. is preferred.
  • the raw material mixture obtained in the mixing step is heat-treated in an oxygen-containing atmosphere (first heat treatment step).
  • the heat-treated product obtained after the first heat treatment step is heat-treated in a reducing gas atmosphere, a mixed gas atmosphere of a reducing gas and an inert gas, or in an inert gas atmosphere (second heat treatment step).
  • pulverization or the like can be performed as necessary so that the infrared absorbing particles have a desired particle size.
  • the infrared absorbing particles of the present embodiment which include the composite tungsten oxide particles obtained by the above steps, have sufficient near-infrared absorbing power and favorable properties as infrared absorbing particles.
  • infrared absorbing particles having excellent long-term storage stability can be obtained.
  • the tungsten compound used in the mixing step includes, for example, tungstic acid (H 2 WO 4 ), ammonium tungstate, tungsten hexachloride, tungsten hexachloride dissolved in alcohol, hydrolyzed by adding water, and then the solvent evaporated. hydrates of, can be used.
  • the M element compound to be subjected to the mixing step for example, one or more selected from oxides, hydroxides, nitrates, sulfates, chlorides, and carbonates of the M element can be used.
  • the material amount ratio (M: W) between the M element (M) and tungsten (W) in the resulting raw material mixture is the desired general It is preferable to blend and mix the ingredients so that x:y in the formula M x W y O z is equal.
  • the mixing method is not particularly limited, and either wet mixing or dry mixing can be used.
  • wet mixing a mixed powder of the element M compound and the tungsten compound is obtained by drying the liquid mixture obtained after wet mixing. Drying temperature and time after wet mixing are not particularly limited.
  • Dry mixing may be carried out using a known mixing device such as a commercially available grinder, kneader, ball mill, sand mill, paint shaker, etc. Mixing conditions such as mixing time and mixing speed are not particularly limited.
  • the heat treatment temperature in the first heat treatment step is not particularly limited, but is preferably higher than the temperature at which the composite tungsten oxide particles crystallize. Specifically, for example, the temperature is preferably 500° C. or higher and 1000° C. or lower, and more preferably 500° C. or higher and 800° C. or lower.
  • Second heat treatment step In the second heat treatment step, heat treatment is performed at a temperature of 500° C. or more and 1200° C. or less in a reducing gas atmosphere, a mixed gas atmosphere of a reducing gas and an inert gas, or an inert gas atmosphere as described above. be able to.
  • the type of reducing gas is not particularly limited, but hydrogen (H 2 ) is preferable.
  • hydrogen when hydrogen is used as the reducing gas, its concentration is not particularly limited and may be appropriately selected according to the firing temperature, the quantity of starting materials, and the like. For example, it is 20 vol% or less, preferably 10 vol% or less, more preferably 7 vol% or less. This is because, if the concentration of the reducing gas is 20 vol % or less, it is possible to avoid the production of WO 2 that does not have a solar radiation shielding function due to rapid reduction.
  • the composite tungsten oxide particles represented by the general formula M x W y O z contained in the infrared absorbing particles of the present embodiment can also be produced by, for example, a plasma method.
  • a plasma method When producing infrared absorbing particles by a plasma method, the following steps can be performed.
  • a raw material mixture of a tungsten compound and an M element compound, or a composite tungsten oxide precursor represented by the general formula MxWyOz ' is prepared (raw material preparation step).
  • the starting material prepared in the material preparation process is supplied into the plasma together with the carrier gas, and through the evaporation and condensation processes, the desired composite tungsten oxide particles are produced (reaction process).
  • the material amount ratio (M: W ) is equal to the ratio x:y of x and y in the aforementioned general formula of the target composite tungsten oxide.
  • the same materials as those described in the solid-phase reaction method can be suitably used, so the description is omitted here.
  • M can be the aforementioned M element
  • W can be tungsten
  • O can be oxygen.
  • ' preferably satisfies 0.001 ⁇ x/y ⁇ 1 and 2.0 ⁇ z'/y.
  • the composite tungsten oxide precursor represented by the general formula MxWyOz ' can be synthesized, for example, by the solid phase reaction method described above.
  • the x/y in the composite tungsten oxide precursor is preferably a material that matches the x/y in the target composite tungsten oxide particles represented by the general formula M x W y O z .
  • a mixed gas of an inert gas and an oxygen gas can be used as the carrier gas for transporting the starting material in the reaction step.
  • Plasma can be generated, for example, in an inert gas alone or in a mixed gas atmosphere of inert gas and hydrogen gas.
  • the plasma is not particularly limited, thermal plasma is preferred.
  • the raw material supplied into the plasma instantly evaporates, the evaporated raw material condenses in the course of reaching the plasma trailing flame, is rapidly cooled and solidified outside the plasma flame, and forms composite tungsten oxide particles.
  • composite tungsten oxide particles having a single crystal phase can be produced.
  • the plasma used in the method for producing infrared-absorbing particles of the present embodiment is, for example, DC arc plasma, high-frequency plasma, microwave plasma, low-frequency AC plasma, or a combination thereof, or a magnetic field is applied to DC plasma. It is preferably obtained by an electrical method, a high-power laser, or a high-power electron beam or ion beam. Whichever thermal plasma is used, it is preferably a thermal plasma having a high temperature zone of 10,000 K or more, more preferably 10,000 K or more and 25,000 K or less, and particularly preferably a plasma capable of controlling the particle generation time.
  • the apparatus shown in FIG. 1 is a hybrid plasma reactor 10 in which a direct current plasma apparatus and a high frequency plasma apparatus are superimposed.
  • the hybrid plasma reactor 10 has a water-cooled quartz double tube 11 and a reaction vessel 12 connected to the water-cooled quartz double tube 11.
  • An evacuation device 13 is connected to the reaction container 12 .
  • a DC plasma torch 14 is provided above the water-cooled quartz double tube 11, and the DC plasma torch 14 is provided with a gas supply port 15 for plasma generation.
  • Sheath gas for high-frequency plasma generation and quartz tube protection can be supplied to the outside of the plasma region along the inner wall of the water-cooled quartz double tube 11 .
  • a sheath gas inlet 16 is provided.
  • a water-cooled copper coil 17 for high-frequency plasma generation is arranged around the water-cooled quartz double tube 11 .
  • a raw material powder carrier gas supply port 18 is provided in the vicinity of the DC plasma torch 14, and is connected by a pipe to a raw material powder supply device 19 that supplies the raw material powder.
  • a gas supply device 20 is connected to the plasma generating gas supply port 15, the sheath gas introduction port 16, and the raw material powder supply device 19 via piping, so that a predetermined gas can be supplied from the gas supply device 20 to each member.
  • a supply port may be provided in addition to the above-mentioned members so as to cool the members in the apparatus or to create a predetermined atmosphere, and connected to the gas supply device 20 .
  • the inside of the reaction system composed of the inside of the water-cooled quartz double tube 11 and the inside of the reaction vessel 12 is evacuated by the evacuation device 13 .
  • the degree of vacuum at this time is not particularly limited, it can be evacuated to, for example, about 0.1 Pa (about 0.001 Torr).
  • argon gas can be supplied from the gas supply device 20 to fill the reaction system with argon gas.
  • the inside of the reaction system is an argon gas flow system of 1 atm.
  • plasma gas can be supplied into the reaction vessel 12 thereafter.
  • the plasma gas is not particularly limited, for example, argon gas, mixed gas of argon and helium (Ar—He mixed gas), mixed gas of argon and nitrogen (Ar—N 2 mixed gas), neon, helium, and xenon. Any gas of choice can be used.
  • the supply flow rate of the plasma gas is also not particularly limited. Then, a DC plasma can be generated.
  • the sheath gas for generating high-frequency plasma and protecting the quartz tube can be spirally supplied from the sheath gas inlet 16 along the inner wall of the water-cooled quartz double tube 11 outside the plasma region.
  • the type of sheath gas and the supply rate are not particularly limited, but for example, argon gas is flowed at 20 L/min or more and 50 L/min or less and hydrogen gas is flowed at 1 L/min or more and 5 L/min or less to generate high frequency plasma.
  • a high frequency power source can be applied to the water-cooled copper coil 17 for high frequency plasma generation.
  • the conditions of the high frequency power source are not particularly limited, for example, a high frequency power source with a frequency of about 4 MHz can be applied at 15 kW or more and 50 kW or less.
  • the raw material can be introduced from the raw material powder carrier gas supply port 18 by the raw material powder supply device 19 using the carrier gas.
  • the carrier gas is also not particularly limited, but for example, a mixed gas consisting of argon gas at 1 L/min or more and 8 L/min or less and oxygen gas at 0.001 L/min or more and 0.8 L/min or less can be used.
  • a raw material mixture that serves as a starting material supplied into the plasma or a composite tungsten oxide precursor is introduced into the plasma and reacted.
  • the supply rate of the starting material from the raw material powder carrier gas supply port 18 is not particularly limited, but is preferably 1 g/min or more and 50 g/min or less, more preferably 1 g/min or more and 20 g/min or less.
  • the supply rate of the starting materials By setting the supply rate of the starting materials to 50 g / min or less, the ratio of the starting materials passing through the center of the plasma flame is sufficiently high, the ratio of unreacted products and intermediate products is suppressed, and the desired composite tungsten
  • the production rate of oxide particles can be increased.
  • productivity can be improved by setting the supply rate of the starting material to 1 g/min or more.
  • the starting material supplied into the plasma instantly evaporates in the plasma, undergoes a condensation process, and forms composite tungsten oxide particles with an average primary particle size of 100 nm or less.
  • the particle size of the composite tungsten oxide particles obtained by the manufacturing method of this embodiment can be easily controlled by the plasma output, plasma flow rate, amount of raw material powder to be supplied, and the like.
  • the produced composite tungsten oxide particles are deposited in the reaction vessel 12 and can be recovered.
  • the surface of the infrared absorbing particles obtained by the manufacturing method described so far can be coated with a coating film. Since the coating film has already been described, the description is omitted here.
  • the method for producing the infrared absorbing particles of the present embodiment has been described above, and the infrared absorbing particles obtained by this production method can be evaluated and confirmed, for example, by the following methods.
  • the analysis method is not particularly limited, for example, M element and tungsten can be analyzed by plasma emission spectrometry, and oxygen can be analyzed by inert gas impulse heating melting infrared absorption method.
  • the crystal structure of the composite tungsten oxide contained in the infrared absorbing particles can be confirmed by powder X-ray diffraction.
  • the particle size of the infrared absorbing particles can be confirmed by TEM observation or particle size measurement based on the dynamic light scattering method.
  • the infrared curable ink composition of this embodiment can contain infrared absorbing particles and a thermosetting resin. It should be noted that the thermosetting resin is preferably in an uncured state, specifically in a fluid state, for example.
  • the infrared curable ink composition 100 of this embodiment can contain the infrared absorbing particles 110 and the thermosetting resin 120 described above.
  • FIG. 3 is a schematic diagram, and the infrared curable ink composition 100 of the present embodiment is not limited to such a form.
  • the infrared absorbing particles 110 are described as spherical particles in FIG. 3, the shape of the infrared absorbing particles 110 is not limited to such a form, and can have any shape.
  • the infrared absorbing particles 110 can also have a coating on their surface as described above.
  • the electromagnetic wave absorbing particle dispersion 10 can also contain additives such as solvents and dispersants, which will be described later, if necessary.
  • Thermosetting resins are not particularly limited, but examples include epoxy resins, urethane resins, acrylic resins, urea resins, melamine resins, phenol resins, ester resins, polyimide resins, and silicone resins. , unsaturated polyester resins and the like can be used.
  • thermosetting resins are hardened by applying heat energy from infrared absorbing particles irradiated with infrared rays, and unhardened resins can be used.
  • the thermosetting resin may contain a monomer or oligomer that forms a thermosetting resin through a curing reaction, and a known curing agent that is appropriately added. Furthermore, a known curing accelerator may be added to the curing agent.
  • (2) Infrared absorbing particles As the infrared absorbing particles, the infrared absorbing particles described above can be used. Since the infrared absorbing particles have already been explained, the explanation is omitted here.
  • the content of the infrared-absorbing particles in the infrared-curable ink composition of the present embodiment is not particularly limited, and can be selected according to the properties required for the infrared-curable ink composition.
  • the amount of the infrared absorbing particles contained in the infrared curable ink composition of the present embodiment may be selected and added so that the uncured thermosetting resin can be cured during the curing reaction. .
  • the infrared absorbing particles are preferably dispersed in an infrared curable ink composition, such as a solvent or the like, which will be described later.
  • the method for dispersing the infrared absorbing particles in the infrared curable ink composition is not particularly limited, but it is preferable to use a wet medium mill or the like.
  • the infrared curable ink composition of the present embodiment can be composed only of the thermosetting resin and the infrared absorbing particles, but can also contain optional components. It can also contain pigments, dyes, dispersants, solvents, etc., which will be described below, depending on the application.
  • the infrared curable ink composition of the present embodiment contains one or more selected from organic pigments, inorganic pigments, and dyes to color the ink composition.
  • the pigment is not particularly limited, and known pigments can be used without particular limitation. More than one type can be preferably used.
  • These pigments are preferably present in a dispersed state in the infrared curable ink composition of the present embodiment.
  • known methods can be used without particular limitation.
  • insoluble pigments are not particularly limited, but examples include azo, azomethine, methine, diphenylmethane, triphenylmethane, quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, azine, oxazine, and thiazine. , dioxazines, thiazoles, phthalocyanines, diketopyrrolopyrroles and the like can be used.
  • organic pigment is not particularly limited, specific pigment names that can be preferably used are listed below.
  • pigments for magenta or red for example, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 48:1, C.I. I. Pigment Red 53:1, C.I. I. Pigment Red 57:1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 139, C.I. I. Pigment Red 144, C.I. I. Pigment Red 149, C.I. I.
  • Pigment Red 166 C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 202, C.I. I. Pigment Red 222, C.I. I. Pigment Violet 19 and the like.
  • pigments for orange or yellow for example, C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 43, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 15:3, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 138 and the like.
  • pigments for green or cyan for example, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like.
  • black pigments for example, C.I. I. Pigment Black 1, C.I. I. Pigment Black 6, C.I. I. Pigment Black 7 and the like.
  • Inorganic pigments are also not particularly limited, but examples include carbon black, titanium dioxide, zinc sulfide, zinc oxide, zinc phosphate, mixed metal oxide phosphate, iron oxide, manganese iron oxide, chromium oxide, ultramarine, and nickel. or chromium antimony titanium oxide, cobalt oxide, aluminum, aluminum oxide, silicon oxide, silicates, zirconium oxide, mixed oxides of cobalt and aluminum, molybdenum sulfide, rutile mixed phase pigments, rare earth sulfides, bismuth vanadate, Extender pigments such as aluminum hydroxide and barium sulfate can be preferably used.
  • the dispersed particle size (average dispersed particle size) of the dispersed pigment contained in the infrared curable ink composition according to the present embodiment is not particularly limited, it is preferably, for example, 1 nm or more and 200 nm or less. This is because when the dispersed particle diameter of the pigment dispersion is 1 nm or more and 200 nm or less, the storage stability in the infrared curable ink composition is particularly good.
  • the dispersed particle size can be measured, for example, with ELS-8000 manufactured by Otsuka Electronics Co., Ltd., which is a particle size measuring device based on the dynamic light scattering method. (3-1-2) Dyes Dyes are not particularly limited, either oil-soluble dyes or water-soluble dyes can be used, and yellow dyes, magenta dyes, cyan dyes, etc. can be preferably used.
  • yellow dyes examples include phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heterylazo dyes having open-chain active methylene compounds as coupling components; azomethine dyes; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes; Dyes, acridine dyes, acridinone dyes and the like can be mentioned.
  • These dyes may exhibit yellow only when a part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal or an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, or a polymer cation having them as a partial structure.
  • magenta dyes examples include aryl or heterylazo dyes having phenols, naphthols, anilines as coupling components; azomethine dyes having pyrazolones, pyrazolotriazoles as coupling components; e.g. arylidene dyes, styryl dyes, merocyanines.
  • methine dyes such as dyes and oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; Cyclic dyes and the like can be mentioned.
  • These dyes may exhibit magenta only when a part of the chromophore is dissociated, and the counter cation in that case may be an inorganic cation such as an alkali metal or ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, or a polymer cation having them as a partial structure.
  • the counter cation in that case may be an inorganic cation such as an alkali metal or ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, or a polymer cation having them as a partial structure.
  • cyan dyes examples include azomethine dyes such as indoaniline dyes and indophenol dyes; polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes; Dyes; anthraquinone dyes; for example, phenols, naphthols, aryl or heteryl azo dyes having anilines as coupling components, and indigo-thioindigo dyes.
  • These dyes may exhibit cyan only when a part of the chromophore is dissociated, and the counter cation in that case may be an alkali metal, an inorganic cation such as ammonium, pyridinium, It may be an organic cation such as a quaternary ammonium salt, or a polymer cation having them as a partial structure.
  • Black dyes such as polyazo dyes can also be used.
  • the water-soluble dye is also not particularly limited, and direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, etc. can be preferably used.
  • Acid Violet 5 34, 43, 47, 48, 90, 103, 126, C.I. Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, 227, C. I.
  • the particle size of the pigment, which is the coloring material in consideration of the characteristics of the application apparatus for the infrared curable ink composition.
  • the infrared curable ink composition of the present embodiment may further contain a dispersant. That is, the above-described infrared absorbing particles may be dispersed together with a dispersant in a thermosetting resin or a solvent, which is an optional component to be described later. By adding a dispersant, the infrared absorbing particles can be easily dispersed in the infrared curable ink composition. In addition, when the coating film of the infrared curable ink composition is cured, the variation in curing can be particularly suppressed.
  • the dispersant used in the near-infrared curable ink composition of the present embodiment is not particularly limited, and for example, any commercially available dispersant can be used.
  • the molecular structure of the dispersant it has a main chain of polyester, polyacrylic, polyurethane, polyamine, polycaptolactone, polystyrene, etc., and functional groups include amino, epoxy, carboxyl, Those having a hydroxyl group, a sulfo group, or the like are preferable.
  • the dispersant having such a molecular structure does not deteriorate when the coating film of the infrared curable ink composition of the present embodiment is intermittently irradiated with infrared rays for several tens of seconds. Therefore, it is possible to particularly suppress the occurrence of defects such as coloring caused by the deterioration.
  • the infrared curable ink composition of the present embodiment can also use a solvent together with the thermosetting resin. That is, the infrared curable ink composition of this embodiment can further contain a solvent.
  • the infrared curable ink composition contains a solvent, infrared absorbing particles and the like are contained and dispersed in the solvent, so the solvent can also be called a dispersion medium.
  • Examples of the solvent for the infrared curable ink composition include water, alcohols such as methanol, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, and diacetone alcohol, and methyl ether, ethyl ether, propyl ether, and the like.
  • Ethers, esters, ketones such as acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, imbutyl ketone, methyl isobutyl ketone, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, polyethylene glycol, polypropylene glycol, etc.
  • Various organic solvents can be used.
  • thermosetting resin monomer in an uncured state together with or instead of the solvent of the infrared curable ink composition.
  • a configuration that does not use a solvent such as an organic solvent can be employed.
  • a solvent for the infrared curable ink composition a functional compound such as an epoxy group that reacts with the monomer or oligomer of the thermosetting resin contained in the thermosetting resin in an uncured state during the curing reaction of the thermosetting resin. It is also preferred to use reactive organic solvents with groups.
  • the infrared curable ink composition of the present embodiment can be prepared, for example, by adding infrared absorbing particles to an uncured thermosetting resin. Further, the infrared curable ink composition of the present embodiment may be prepared by dispersing the infrared absorbing particles in an appropriate solvent and then adding an uncured thermosetting resin.
  • the infrared curable ink composition of the present embodiment can contain composite tungsten oxide particles as infrared absorbing particles.
  • the infrared curable ink composition of this embodiment can be, for example, an infrared curable ink composition containing infrared absorbing particles, a solvent, a dispersant, and a thermosetting resin.
  • the solvent can also be removed from the infrared curable ink composition at the time of use or the like.
  • the infrared curable ink composition of the present embodiment may contain composite tungsten oxide particles as infrared absorbing particles, a dispersant, and a thermosetting resin.
  • the infrared-curable ink composition of the present embodiment contains the infrared-absorbing particles described above, for example, when it is applied onto a substrate and irradiated with infrared rays to form a cured product (cured product), it is more neutral. color tone.
  • the infrared-absorbing particles have excellent near-infrared absorption characteristics, they can supply sufficient heat when irradiated with near-infrared rays, etc., and can sufficiently improve the adhesion of the resulting cured product to the substrate. .
  • the infrared curable ink composition of the present embodiment can be used for conventional ink applications that form an infrared curable film on a substrate. Further, the infrared curable ink composition of the present embodiment can also be applied to stereolithography in which a three-dimensional object is formed by applying a predetermined amount of the infrared ray curable ink composition onto a substrate, irradiating the substrate with infrared rays, curing the composition, and stacking the composition. .
  • the viscosity can be adjusted, so that the handleability can be improved when applying to a substrate or the like.
  • the infrared curable ink composition of this embodiment does not have to contain a solvent.
  • the infrared curable ink composition of the present embodiment can contain, for example, infrared absorbing particles, a thermosetting resin, and, if necessary, a dispersant and the like. Since the infrared curable ink composition of the present embodiment does not contain a solvent, it is possible to omit the operation of volatilizing the solvent, etc., so that the efficiency of curing the coated material of the infrared curable ink composition can be improved. can.
  • the method for removing the solvent after applying the near-infrared curable ink composition is not particularly limited. etc. can be used.
  • the infrared cured product of the present embodiment can be a cured product of the infrared curable ink composition described above.
  • the infrared cured product of the present embodiment may be placed on a substrate, or may exist alone without including a substrate or the like.
  • the substrate will be described in the method for producing an infrared cured product below.
  • the infrared cured product of the present embodiment may have a film shape, or may have a three-dimensional shape such as a three-dimensional shape. When it has a film shape, the infrared cured product of the present embodiment can also be called an infrared cured film.
  • the infrared-cured product of the present embodiment can be produced, for example, by a method for producing an infrared-cured product having a coating step and a curing step, which will be described below. According to the method for producing an infrared cured product of the present embodiment, the infrared cured product described above can be produced.
  • the infrared curable ink composition described above can be applied to form a coating.
  • the solvent and the like can be removed as necessary.
  • the coating can be cured by irradiating it with infrared rays.
  • the application step and the curing step can be repeated, and an infrared cured product having a desired shape and size can be obtained.
  • the infrared cured product can also have a film shape.
  • the infrared cured product can be called an infrared cured film, and the method for producing the infrared cured product can also be called a method for producing an infrared cured film.
  • an infrared cured product which is a three-dimensional object, can be modeled and produced on a substrate.
  • an infrared-cured product is obtained by irradiating an infrared ray to a coated product obtained by, for example, coating an infrared-curable ink composition on a substrate in the above steps. be done.
  • the infrared-absorbing particles in the infrared-curable ink composition absorb the irradiated infrared rays to generate heat, and the generated thermal energy is converted into a polymerization reaction by monomers, oligomers, etc. contained in the uncured thermosetting resin. This is because reactions such as condensation reaction, addition reaction, etc. are accelerated, and a curing reaction of the thermosetting resin occurs.
  • the solvent can also volatilize due to the heat generation of the infrared absorbing particles due to the irradiation of the infrared rays in the curing step.
  • the infrared curable film of the present embodiment contains a thermosetting resin obtained by curing the uncured thermosetting resin in the infrared curable ink composition. , because it does not re-melt.
  • This characteristic is applied to stereolithography in which the infrared curable ink composition of the present embodiment is cured and stacked, and the application of the infrared curable ink composition and the irradiation of infrared rays are repeated to repeat lamination to form a three-dimensional object. It is particularly effective when
  • Coating step for example, the above-described infrared curable ink composition can be applied onto a substrate to form a coating film.
  • the material of the substrate (substrate) to which the infrared curable ink composition is applied is not particularly limited.
  • the substrate for example, one or more substrates selected from paper, resin, glass, etc. can be used.
  • polyester such as PET (polyethylene terephthalate), acrylic, urethane, polycarbonate, polyethylene, ethylene vinyl acetate copolymer, vinyl chloride, fluororesin, polyimide, polyacetal, polypropylene, and nylon. etc. can be used.
  • the shape of the substrate is not particularly limited, and can be a shape that matches the shape required for the infrared cured product, such as a plate shape.
  • the method of applying the infrared curable ink composition to the substrate surface is not particularly limited, but dipping method, flow coating method, spray method, bar coating method, spin coating method, gravure coating method, roll coating method, screen printing method, blade A coating method or the like can be used.
  • the infrared curable ink composition can be cured by irradiating the coated article with infrared rays. By carrying out the curing step, an infrared cured product can be produced.
  • infrared irradiation is preferable, and near-infrared irradiation is more preferable.
  • Infrared rays have a high energy density and can efficiently impart the energy necessary for curing the resin in the infrared curable ink composition.
  • infrared irradiation it is also preferable to combine infrared irradiation with any method selected from known methods to cure the infrared curable ink composition.
  • methods such as heating, air blowing, and electromagnetic wave irradiation may be used in combination with infrared irradiation.
  • infrared rays refer to electromagnetic waves having a wavelength in the range of 0.75 ⁇ m or more and 1 mm or less
  • near infrared rays refer to infrared rays with wavelengths of 0.75 ⁇ m or more and 4 ⁇ m or less
  • far infrared rays have a wavelength of 4 ⁇ m or more and 1000 ⁇ m.
  • the infrared curable ink composition can be cured and similar effects can be obtained regardless of which infrared rays, generally called far infrared rays or near infrared rays, are applied. However, in the case of irradiation with near-infrared rays, the coating film can be cured efficiently in a shorter time.
  • microwaves can be suitably used as such electromagnetic waves.
  • the microwave refers to an electromagnetic wave having a wavelength in the range of 1 mm or more and 1 m or less.
  • the irradiated microwave preferably has a power of 200 W or more and 1000 W or less. If the power is 200 W or more, vaporization of the solvent remaining in the infrared curable ink composition is accelerated.
  • the infrared irradiation time for the infrared curable ink composition is not particularly limited, depending on the energy and wavelength of the irradiation, the composition of the infrared curable ink composition, and the coating amount of the infrared curable ink composition.
  • the infrared irradiation time is generally preferably 0.1 second or longer. By setting the irradiation time to 0.1 seconds or more, it is possible to perform sufficient infrared irradiation to cure the infrared curable ink composition.
  • the irradiation time for example, it is possible to sufficiently dry the solvent in the infrared absorbing curable ink composition, but considering high-speed printing and coating, the irradiation time should be within 30 seconds. and more preferably within 10 seconds.
  • the infrared radiation source is not particularly limited, and infrared radiation may be obtained directly from a heat source, or a heat medium may be interposed to obtain effective infrared radiation therefrom.
  • infrared rays can be obtained by using discharge lamps such as mercury, xenon, cesium, and sodium, carbon dioxide lasers, and heating of electric resistors such as platinum, tungsten, nichrome, and kanthal.
  • Halogen lamps and laser beams are preferred radiation sources.
  • Halogen lamps have advantages such as good thermal efficiency and quick start-up.
  • Irradiation of the infrared ray to the coated material may be performed from the side of the substrate coated with the infrared curable ink composition or from the back side. It is also preferable to irradiate from both sides at the same time, and it is also preferable to combine with temperature-rising drying or air-blowing drying. Moreover, it is more preferable to use a condensing plate as needed. By combining these methods, it is possible to cure the infrared curable ink composition with short-time infrared irradiation.
  • an infrared cured film which is a film-like infrared cured product
  • a three-dimensional object can also be formed by repeatedly laminating cured products of the infrared curable ink composition. That is, it is also possible to produce an infrared cured product having a desired three-dimensional structure by repeating the coating step and the irradiation step described above.
  • stereolithography can be carried out. That is, it is also possible to adopt a stereolithography method that includes the coating process described above and the curing process.
  • the infrared-absorbing particles contained in the infrared-curable ink composition used for producing the infrared-cured product of the present embodiment have visible light transmittance, a transparent infrared-shielding film can be easily obtained by curing with infrared rays. can be done.
  • At least one of various pigments and dyes can be added to the infrared curable ink composition.
  • a colored film can be easily obtained by using an infrared curable ink composition containing such a pigment.
  • the color is hardly affected by the infrared absorbing particles, so that it can be used for a color filter of a liquid crystal display or the like.
  • the pigments and the like that can be preferably used when obtaining the colored film have already been described in the infrared ray curable ink composition, so description thereof will be omitted here.
  • Cs was evaluated with a flame atomic absorption spectrophotometer (manufactured by VARIAN, model: SpectrAA 220FS). W was evaluated by an ICP emission spectrometer (manufactured by Shimadzu Corporation, model: ICPE9000). O was evaluated by an oxygen-nitrogen simultaneous analyzer (manufactured by LECO, model: ON836). K and Rb were also evaluated in the same manner as Cs.
  • the X-ray diffraction pattern of the composite tungsten oxide particles obtained by removing the solvent from the infrared-absorbing particle dispersion liquid prepared in the following Examples and Comparative Examples was analyzed using the powder X-ray diffractometer. It was measured by the X-ray diffraction method. Then, from the obtained X-ray diffraction pattern, the crystallite size of the composite tungsten oxide was calculated using the Rietveld method. (3) Peel test of infrared cured film, evaluation of long-term storage stability 100 grid-shaped cuts were made on the infrared cured film obtained in the following examples and comparative examples using a cutter guide with a gap interval of 1 mm.
  • An infrared curable ink composition and an infrared curable film were prepared under the same conditions, except that the infrared absorbing particle dispersion containing the infrared absorbing particles was stored at room temperature for 3 months, and a peeling test was performed in the same manner. The results of the peeling test were used as evaluations of long-term storage stability. (Experimental example) Hereinafter, manufacturing conditions for samples in Examples and Comparative Examples will be described.
  • Example 1 (Preparation of infrared absorbing particles) 23.5 g of Cs 2 CO 3 was dissolved in 36 g of water, and this was added to 109 g of H 2 WO 4 and thoroughly stirred, followed by drying to obtain a raw material mixture according to Example 1 (raw material preparation step).
  • the reaction process was carried out using the hybrid plasma reactor 10 shown in FIG. 1 in which DC plasma and high-frequency plasma were superimposed.
  • the inside of the reaction system was evacuated to approximately 0.1 Pa (approximately 0.001 torr) by the evacuation device 13, and then completely replaced with argon gas to form an argon flow system of 1 atm.
  • the high frequency power input at this time was 45 kW.
  • 2 g of the raw material mixture according to Example 1 was supplied from the raw material powder supply device 19 using a mixed gas of 3 L/min of argon gas and 0.01 L/min of oxygen gas as a carrier gas. /min into the plasma.
  • the particle diameters of the recovered cesium tungsten oxide particles a were determined by TEM observation, it was confirmed that the particle diameters of the 30 evaluated particles were 10 nm or more and 50 nm or less.
  • the diameter of the particle was calculated by taking the diameter of the smallest circle circumscribing the particle to be evaluated as the particle diameter of the particle.
  • the particle diameter of the infrared absorbing particles is evaluated under the same conditions and method.
  • the crystal structure of the compound contained in the tungsten cesium oxide particles a when the crystal structure of the compound contained in the tungsten cesium oxide particles a was identified, the same peak as that of hexagonal Cs 0.3 WO 3 was confirmed. As described above, the crystal structure of the obtained composite tungsten oxide can be identified from the X-ray diffraction pattern. In the case of this example, the crystal structure of the compound contained in the composite tungsten oxide particles as described above matches the peak of the similar hexagonal composite tungsten oxide. Therefore, it can be confirmed that the crystal structure of the composite tungsten oxide obtained in this example, that is, cesium tungsten oxide, is hexagonal.
  • the dispersed particle size of the cesium tungsten oxide particles (a-1) in the A-1 liquid was measured by a particle size measuring device (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.) based on the dynamic light scattering method, 80 nm.
  • the crystallite size of the cesium tungsten oxide particles (a-1) after the liquid A-1 was fractionated and the solvent was removed was 24 nm.
  • the particle diameter, dispersed particle diameter, and crystallite diameter of the infrared-absorbing particles were evaluated in the same manner as in the case of the above-described dispersion liquid. was confirmed.
  • the particle diameter, dispersed particle diameter, and crystallite diameter of the infrared-absorbing particles in the infrared-curable ink composition are the same as the evaluation results of the infrared-absorbing particles after production and the dispersion liquid. It has become.
  • Liquid A-1 was heated to 70° C. and kept for 500 hours while stirring. Thereafter, after removing the solvent from the A-1 solution, it was dried under a nitrogen atmosphere. 20% by mass of the resulting dry powder, 65% by mass of methyl isobutyl ketone, and 15% by mass of an acrylic dispersant were weighed and charged into a paint shaker (manufactured by Asada Iron Works Co., Ltd.) containing 0.3 mm ⁇ ZrO beads. An infrared absorbing particle dispersion (A-2) was prepared by crushing for minutes.
  • This infrared curable ink composition was applied onto a glass plate using a bar coater (No. 10) to form a coated product (coating film) (coating step).
  • a line heater HYP-14N (output 980 W) manufactured by HYBEC Co., Ltd. was installed at a height of 5 cm from the coated surface, and the coated material was irradiated with infrared rays for 10 seconds to obtain an infrared cured film. (hardening process). (Initial peeling test) The resulting cured film was visually confirmed to be transparent.
  • the evaluation result was ⁇ .
  • thermosetting ink composition after storage for 3 months.
  • a commercially available one-liquid type uncured epoxy resin thermosetting ink manufactured by Teikoku Ink Mfg. Co., Ltd., MEG screen ink (medium (clear)
  • MEG screen ink medium (clear)
  • an infrared curable film was prepared in the same manner except that the infrared curable ink composition was used, and a peeling test was performed on the infrared curable film.
  • the evaluation results are shown in the column of "Evaluation after storage" in Table 1. [Example 2] Using the high frequency plasma reactor 30 shown in FIG. 2, infrared absorbing particles were prepared.
  • the high-frequency plasma reactor 30 has a water-cooled quartz double tube 31 and a reaction vessel 32 connected to the water-cooled quartz double tube 31 .
  • a vacuum evacuation device 33 is connected to the reaction container 32 .
  • a gas supply port 34 for plasma generation is provided above the water-cooled quartz double tube 31 .
  • a sheath gas for generating high-frequency plasma and protecting the quartz tube can be supplied. is provided.
  • a water-cooled copper coil 37 for high-frequency plasma generation is arranged around the water-cooled quartz double tube 31 .
  • a raw material powder carrier gas supply port 38 is provided in the vicinity of the plasma generation gas supply port 34, and is connected by a pipe to a raw material powder supply device 39 that supplies the raw material powder.
  • the plasma generating gas supply port 34, the sheath gas introduction port 36, and the raw material powder supply device 39 can be connected to the gas supply device 40 via piping so that a predetermined gas can be supplied from the gas supply device 40 to each member.
  • a supply port may be provided in addition to the above-mentioned members so as to cool the members in the apparatus or to create a predetermined atmosphere, and connected to the gas supply device 40 .
  • the raw material mixture prepared in Example 1 is supplied from the raw material powder supply device 39 to plasma at a rate of 2 g/min. supplied inside.
  • the particle diameter of the infrared absorbing material particles collected at the bottom of the reaction vessel 32 was 10 nm or more and 50 nm or less from TEM observation.
  • the X-ray diffraction pattern of the cesium tungsten oxide particles which are the infrared-absorbing particles according to Example 2, was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method).
  • ⁇ -2 ⁇ method powder X-ray diffraction method
  • Example 1 an infrared curable ink composition and an infrared curable film were prepared and evaluated in the same manner as in Example 1, except that the infrared absorbing particles according to Example 2 were used. Table 1 shows the evaluation results.
  • Example 3 Example 3 was carried out in the same manner as in Example 2, except that a mixed gas of argon gas at 5 L/min and oxygen gas at 0.01 L/min was used as the carrier gas when supplying the raw material mixture. was prepared and evaluated.
  • the particle diameter of the infrared absorbing particles recovered from the high-frequency plasma reactor 30 was 10 nm or more and 50 nm or less by TEM observation.
  • the X-ray diffraction pattern of the obtained infrared absorbing particles according to Example 3 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was specified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Cs 0.3 WO 3 was confirmed.
  • Example 1 an infrared curable ink composition and an infrared curable film were prepared and evaluated in the same manner as in Example 1, except that the infrared absorbing particles according to Example 3 were used. Table 1 shows the evaluation results.
  • Example 4 Example 4 was carried out in the same manner as in Example 2, except that a mixed gas of 4 L/min of argon gas and 0.01 L/min of oxygen gas was used as the carrier gas when supplying the raw material mixture. was prepared.
  • the particle diameter of the infrared absorbing particles recovered from the high-frequency plasma reactor 30 was 10 nm or more and 50 nm or less by TEM observation.
  • the X-ray diffraction pattern of the obtained infrared absorbing particles according to Example 4 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was specified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Cs 0.3 WO 3 was confirmed.
  • Example 1 an infrared curable ink composition and an infrared curable film were prepared and evaluated in the same manner as in Example 1, except that the infrared absorbing particles according to Example 4 were used. Table 1 shows the evaluation results.
  • Example 5 13 g of K 2 CO 3 was dissolved in 59 g of water, and this was added to 180 g of H 2 WO 4 and thoroughly stirred, followed by drying to obtain a raw material mixture according to Example 5.
  • the raw material mixture according to Example 5 was supplied into the plasma in the same manner as in Example 2 to obtain a powder of K 0.27 WO 3.14 particles, which are the infrared absorbing particles according to Example 5.
  • the particle diameter of the collected infrared absorbing particles was 10 nm or more and 50 nm or less by TEM observation.
  • the X-ray diffraction pattern of the obtained infrared absorbing particles according to Example 5 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was specified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal K 0.27 WO 3 was confirmed.
  • Example 1 An infrared curable ink composition and an infrared curable film were prepared and evaluated in the same manner as in Example 1, except that the infrared absorbing particles according to Example 5 were used. Table 1 shows the evaluation results.
  • Example 6 22.17 g of Rb 2 CO 3 was dissolved in 50 g of water, and this was added to 150 g of H 2 WO 4 and thoroughly stirred and then dried to obtain a raw material mixture according to Example 6.
  • the raw material mixture according to Example 6 was supplied into the plasma in the same manner as in Example 2 to obtain a powder of Rb 0.3 WO 3.16 particles, which are the near-infrared absorbing particles according to Example 6.
  • the particle diameter of the collected infrared absorbing particles was 10 nm or more and 50 nm or less by TEM observation.
  • the X-ray diffraction pattern of the obtained infrared absorbing particles according to Example 6 was measured by a powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was specified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Rb 0.3 WO 3 was confirmed.
  • Example 6 an infrared curable ink composition and an infrared curable film were prepared and evaluated in the same manner as in Example 1, except that the infrared absorbing particles according to Example 6 were used.
  • Example 1 the solvent was removed from the infrared-absorbing particle dispersion, and the composite tungsten oxide particles, which are the infrared-absorbing particles recovered from the dispersion, had a crystallite diameter of 23.9 nm and a lattice constant of , the a-axis was 7.3958 ⁇ and the c-axis was 7.5605 ⁇ .
  • the cesium tungsten oxide particles a obtained in Example 1 were sintered at 500° C. for 1 hour in a 3% H 2 gas atmosphere with N 2 gas as a carrier gas to prepare infrared absorbing particles according to Comparative Example 1.
  • the infrared absorbing particles according to Comparative Example 1 are coarser than the infrared absorbing particles according to Example 1 due to the effect of firing at 500 ° C. for 1 hour in a 3% H 2 gas atmosphere. - The pulverization time was 2 hours.
  • Example 1 an infrared curable ink composition and an infrared curable film were prepared and evaluated in the same manner as in Example 1, except that the above infrared absorbing particle dispersion was used in place of Liquid A-1 of Example 1. Table 1 shows the evaluation results.
  • Example 1 the X-ray diffraction pattern of the obtained infrared absorbing particles according to Comparative Example 1 was measured by the powder X-ray diffraction method ( ⁇ -2 ⁇ method). When the crystal structure contained in the particles was specified from the obtained X-ray diffraction pattern, the same peak as that of hexagonal Cs 0.3 WO 3 was confirmed.
  • Example 1 the solvent was removed from the infrared absorbing particle dispersion liquid, and the crystallite size of the composite tungsten oxide particles, which were the infrared absorbing particles recovered, was 9 nm, and the lattice constant thereof was 7 on the a-axis. .4100 ⁇ and the c-axis was 7.6300 ⁇ .
  • the infrared curable ink compositions of Examples 1 to 6 showed no significant change in the infrared absorption characteristics even after storage for 3 months. It was confirmed that an infrared cured film having excellent adhesion to the substrate could be produced by curing. On the other hand, the infrared curable ink composition according to Comparative Example 1 exhibited a decrease in infrared absorption characteristics after storage for 3 months. be done.
  • Infrared curable ink composition 110 Infrared absorbing particles 120 Thermosetting resin

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PCT/JP2022/032099 2021-08-27 2022-08-25 赤外線硬化型インク組成物、赤外線硬化物、赤外線硬化物の製造方法 Ceased WO2023027157A1 (ja)

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