TWI808930B - Near infrared curable composition for ink printing, near infrared cured film, and stereolithography - Google Patents

Abstract

The present invention provides a near-infrared curable ink composition containing a near-infrared absorber having sufficient near-infrared absorption and excellent transparency, a near-infrared curable film, and a photolithography method using the near-infrared curable ink composition. The present invention provides a near-infrared-curable ink composition comprising composite tungsten oxide as near-infrared-absorbing fine particles and an uncured thermosetting resin, a near-infrared curable film, and optical modeling using the near-infrared-curable ink composition Law.

Description

Near-infrared ray-curable composition for ink printing, near-infrared ray-curable film, and photoforming method

The invention relates to a near-infrared hardening ink composition, a near-infrared hardening film and a light shaping method.

In recent years, ultraviolet curable paints that are cured by ultraviolet light can be printed without heating, and thus are widely known as environmentally friendly paints (Patent Documents 1 to 6).

However, when a composition that undergoes radical polymerization by ultraviolet irradiation is used as an ultraviolet curable ink or paint, the presence of oxygen hinders polymerization (hardening). Also, when using a composition that is cationically polymerized by irradiation with ultraviolet rays, 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, ultraviolet absorbers are generally used, but when ultraviolet absorbers are used in ultraviolet curable inks or coatings, there is a possibility that the hardening by ultraviolet irradiation will be hindered. question.

In order to solve these problems, Patent Documents 7 and 8 propose a near-infrared curable composition that is cured by irradiation of near-infrared rays instead of ultraviolet rays.

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 7-100433

[Patent Document 2] Japanese Patent No. 3354122

[Patent Document 2] Japanese Patent No. 5267854

[Patent Document 3] Japanese Patent No. 5626648

[Patent Document 4] Japanese Patent No. 3494399

[Patent Document 6] Japanese Patent Laid-Open No. 2004-18716

[Patent Document 7] Japanese Patent No. 5044733

[Patent Document 8] Japanese Patent Laid-Open No. 2015-131928

However, according to studies by the inventors of the present invention, all of the above-mentioned near-infrared curable compositions have a problem of insufficient near-infrared absorption characteristics.

The present invention was made in order to solve the above problems, and its object is to provide a near-infrared curable ink composition containing a near-infrared absorber having sufficient near-infrared absorption and excellent transparency, a near-infrared cured film, and an ink composition using the near-infrared curable film. Photoforming method of near-infrared curable ink composition.

The inventors of the present invention conceived of a near-infrared curable ink composition containing composite tungsten oxide as near-infrared-absorbing fine particles. Since the composite tungsten oxide fine-particles have high near-infrared-absorbing properties, heat generated by the absorption is used for thermal curing. The permanent resin is cured efficiently, and the present invention has been completed.

That is, the first invention for solving the above-mentioned problems is A near-infrared curable ink composition is characterized in that it contains composite tungsten oxide as near-infrared absorbing fine particles and uncured thermosetting resin.

The second invention is the near-infrared curable ink composition as described in the first invention, characterized in that it further contains a dispersant.

The third invention is the near-infrared curable ink composition according to the first or second invention, characterized in that it further contains a solvent.

The fourth invention is the near-infrared curable ink composition according to any one of the first to third inventions, wherein the dispersed particle size of the near-infrared absorbing fine particles is 1 nm to 800 nm.

The fifth invention is the near-infrared curable ink composition according to any one of the first to fourth inventions, wherein the near-infrared absorbing fine particles include composite tungsten oxide, and include a hexagonal crystal structure or all of them. The crystal structure of hexagonal crystal.

The 6th invention is the near-infrared curable ink composition described in any one of the 1st to 5th inventions, characterized in that: the composite tungsten oxide has the general formula M _x W _y O _z (the M element is selected from 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, I One or more elements among them, W is tungsten, O is oxygen, and 0.001≦x/y≦1, 2.2≦z/y≦3.0).

The seventh invention is the near-infrared curable ink composition as described in the sixth invention, characterized in that: the composite tungsten oxide contains M elements selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr Composite tungsten oxides of one or more of Fe, Sn.

The eighth invention is the near-infrared curable ink composition as described in the first to seventh inventions, characterized in that the surface of the near-infrared absorbing fine particles is composed of any one or more elements of Si, Ti, Zr, and Al. oxide coating.

The ninth invention is the near-infrared curable ink composition as described in the first to eighth inventions, characterized in that it further contains any one or more selected from organic pigments, inorganic pigments, and dyes.

The tenth invention is a near-infrared curable film characterized in that the near-infrared curable ink composition according to any one of the first to ninth inventions is cured by irradiation with near-infrared rays.

The eleventh invention is a photolithography method characterized by applying the near-infrared curable ink composition according to any one of the first to ninth inventions to form a coated object, and irradiating the coated object with near-infrared rays. to make it harden.

The near-infrared-curable ink composition of the present invention has high near-infrared absorption characteristics and excellent transparency, and is industrially useful as a near-infrared-curable ink composition.

Hereinafter, the near-infrared curable ink composition, near-infrared curable film, and photolithography method of the present invention will be described in detail.

1. Near-infrared absorbing microparticles

As the near-infrared absorbing fine particles, carbon black powder or tin-doped indium oxide (ITO) powder can be considered, including fine particles of composite tungsten oxide.

However, if carbon black powder is used, since the carbon black powder is black, the degree of freedom of selection of the color of the near-infrared curable ink composition is low. On the other hand, if a large amount of ITO powder is not added, the curability of the near-infrared curable ink composition cannot be exhibited. Therefore, if a large amount is added, the color tone of the near-infrared curable ink composition will be affected due to the large amount of ITO powder added.

Based on the above, the present invention is characterized by including composite tungsten oxide as near-infrared absorbing fine particles. By using it as a composite tungsten oxide, free electrons are generated in the composite tungsten oxide, and absorption characteristics from free electrons are shown in the near-infrared region, and it is effective as near-infrared-absorbing fine particles near a wavelength of 1000nm.

The dispersed particle size of the near-infrared absorbing microparticles of the present invention is preferably 800 nm or less. The reason for this is that near-infrared absorption of composite tungsten oxide, which is a near-infrared-absorbing fine particle, is based on light absorption and scattering unique to nanoparticles called "localized surface plasmon resonance". That is, the reason is that when the dispersed particle size of the composite tungsten oxide is 800 nm or less, localized surface plasmon resonance occurs, and near-infrared rays irradiated to the near-infrared-curable ink composition of the present invention are effectively absorbed by the near-infrared rays. Efficiently absorbed and easily converted into heat energy.

When the dispersed particle size is 200 nm or less, the localized surface plasmon resonance becomes stronger and absorbs irradiated near-infrared rays more strongly, which is more preferable.

Furthermore, from the viewpoint of near-infrared absorption characteristics and transparency maintenance, the dispersed particle size of the near-infrared absorption fine particles of the present invention is more preferably 200 nm or less. Furthermore, the reason is that near-infrared rays irradiated to the near-infrared ray-curable ink composition of the present invention are efficiently absorbed by the near-infrared ray-absorbing fine particles and easily converted into heat energy when the dispersed particle diameter is 200 nm or less.

In addition, even when the coating of the near-infrared curable ink composition of the present invention does not contain any coloring materials such as pigments, it appears light blue due to the composite tungsten fine particles of the near-infrared absorbing fine particles of the present invention. However, if the dispersed particle size of the fine particles is 200nm or less, the bluish coloration can be eliminated by coloring materials such as pigments.

The dispersed particle size of the near-infrared absorbing microparticles of the present invention is preferably 50 nm or less. The reason for this is that if the dispersed particle size is less than 50 nm, scattering of light due to Mie scattering and Rayleigh scattering of fine particles is sufficiently suppressed, and transparency in the visible wavelength region can be maintained.

If the near-infrared-absorbing microparticles can maintain transparency in the visible light wavelength region, when adding a coloring material such as a pigment to the near-infrared-curable ink composition of the present invention, the freedom to adjust the color tone can be ensured without impairing the color development of the pigment. Spend. On the other hand, even when the above-mentioned coloring material is not added to the near-infrared curable ink composition of the present invention, the transparency of the photo-shaped object as a cured product described later can be ensured.

Here, the so-called dispersed particle size refers to the aggregated particle size of the near-infrared absorbing microparticles containing composite tungsten oxide in the solvent, which can be measured by various commercially available particle size distribution meters. And measure. For example, in a state where there is also an aggregate of near-infrared-absorbing microparticles containing composite tungsten oxide, a sample can be sampled from a dispersion in which near-infrared-absorbing microparticles containing composite tungsten oxide are dispersed in a solvent, and can be sampled using dynamic light scattering The method is based on the principle of ELS-800 manufactured by Otsuka Electronics Co., Ltd. and measured.

In addition, the above-mentioned composite tungsten oxide is effective as a near-infrared ray absorbing material when it has a structure of tungsten bronze such as tetragonal crystal, cubic crystal, and hexagonal crystal. According to the crystal structure of the composite tungsten oxide, there is a tendency for the absorption position in the near-infrared region to change. The absorption position in the near-infrared region tends to move to the long-wavelength side in the case of the tetragonal crystal compared with the cubic crystal, and then in the Hexagonal crystal tends to move to the longer wavelength side than tetragonal crystal. Also, as the absorption position changes, hexagonal crystals have the least absorption in the visible light region, followed by tetragonal crystals, and cubic crystals are the largest among them. Therefore, it is better to use hexagonal tungsten bronze for applications that transmit more light in the visible light region and shield more light in the infrared region. However, the tendency of the optical properties described here is always an approximate tendency, and it may vary depending on the kind of added elements, the added amount, or the amount of oxygen, and the present invention is not limited thereto.

The above-mentioned composite tungsten oxide is preferably of the general formula M _x W _y O _z (M is selected from 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, One or more elements of Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, W is tungsten, O is oxygen, and 0.001≦x/y≦1, 2.2≦ z/y≦3.0).

Here, by controlling the amount of oxygen and adding elements that generate free electrons to the composite tungsten oxide, near-infrared absorbing fine particles with higher efficiency can be obtained. When the general formula of the composite tungsten oxide that has been used to control the amount of oxygen and add elements that generate free electrons is described as M _x W _y O _z (wherein, M is the above-mentioned M element, W is tungsten, and O is oxygen), It is more ideal to satisfy the relationship of 0.001≦x/y≦1, 2.2≦z/y≦3.0.

First, the value of x/y indicating the addition amount of the element M will be described. If the value of x/y is greater than 0.001, a sufficient amount of free electrons can be generated to obtain the near-infrared shielding effect of the target. Furthermore, as the amount of element M added increases, the supply of free electrons increases and the near-infrared absorption efficiency also increases, but this effect is also saturated when the value of x/y is around 1. Also, when the value of x/y is less than 1, it is preferable to avoid the generation of impurity phases in the near-infrared absorbing fine particles. Also, the element M is preferably selected from 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, One or more of Re, Be, Hf, Os, Bi, I. Here, from the viewpoint of stability, the element M in the M _x W _y O _z to which the element M has been added is more preferably selected from 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 at least one element.

Next, the value of z/y representing the control of the oxygen amount will be described. The value of z/y is preferably 2.2≦z/y≦3.0 because there is also a supply of free electrons based on the addition amount of the above-mentioned element _M in the infrared-absorbing fine particles expressed by M _x W _y O z.

In order to obtain the effect of improving the transmission of the visible light region and improving the absorption of the near-infrared region of the present invention, as long as the unit structure (6 octahedrons formed by WO ₆ units are assembled to form hexagonal voids) is included in the composite tungsten oxide , the structure in which the element M is disposed in the gaps), the composite tungsten oxide particles can be either crystalline or amorphous.

When cations of the element M are added to the voids of the hexagons, the absorption in the near-infrared region increases. Here, in general, the hexagonal crystal is formed when an element M with a larger ionic radius is added, specifically, when Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn are added When more than one kind is easy to form a hexagonal crystal, it is preferable. Of course, regarding elements other than these, as long as the additive element M exists in the interstices of the hexagon formed by the WO ₆ unit, it is not limited to the above-mentioned elements.

In particular, when the composite tungsten oxide having a hexagonal crystal structure has a uniform crystal structure, the addition amount of the additional element M is preferably 0.2 or more and 0.5 or less in terms of the value of x/y, and more preferably It is 0.30~0.35. In particular, when the value of x/y becomes 0.33, the additive element M is considered to be arranged in the entire area of the hexagonal void. Also, from the viewpoint of improving the weather resistance of the near-infrared-absorbing fine particles, it is preferable that the surface of the near-infrared-absorbing fine particles of the present invention be coated with an oxide containing one or more of Si, Ti, Zr, and Al.

2. Manufacture of near-infrared absorbing microparticles

The above-mentioned composite tungsten oxide can be obtained by heat-treating a mixture of a tungsten compound and M element as a starting material of the composite tungsten oxide in a reducing gas environment, a mixed gas environment of a reducing gas and an inert gas, or an inert gas environment. get. The composite tungsten oxide microparticles obtained through this heat treatment have the property that they have sufficient near-infrared absorption force and are preferable as near-infrared absorption microparticles.

The tungsten compound as the starting material is preferably selected from tungsten trioxide powder, tungsten dioxide powder, or tungsten oxide hydrate, or tungsten hexachloride powder, or tungsten Ammonium acid powder, or tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then drying, or dissolving tungsten hexachloride in alcohol, adding water to precipitate and drying Any one or more of the obtained tungsten oxide hydrate powder, the tungsten compound powder obtained by drying the ammonium tungstate aqueous solution, and the metal tungsten powder.

These raw materials are used and heat-treated in a reducing gas environment or a mixed gas environment of a reducing gas and an inert gas, or an inert gas environment to obtain near-infrared-absorbing microparticles containing composite tungsten oxides.

In addition, the element M of the above-mentioned composite tungsten oxide fine particles uses a tungsten compound contained as a single element or a compound as a starting material. Here, in order to manufacture the tungsten compound as the starting material for uniformly mixing the components at the molecular level, it is preferable to mix the raw materials in a solution, and the tungsten compound containing the element M is preferably soluble in water or an organic solvent, etc. Those in solvents. For example, tungstates, chloride salts, nitrates, sulfates, oxalates, oxides, carbonates, hydroxides, etc. containing element M can be listed, but not limited to these, if it is in the form of a solution , is better.

The raw materials for producing the above-mentioned composite tungsten oxide fine particles will be described again in detail below.

Here, as the heat treatment condition of the composite tungsten oxide microparticles in an inert gas atmosphere, it is more than 600°C, preferably 650°C or more. The starting material heat-treated at 650° C. or higher has sufficient near-infrared absorption, and is efficient as near-infrared-absorbing fine particles. As the inert gas, it is preferable to use inert gases such as Ar and N ₂ . Also, as heat treatment conditions in a reducing gas environment or a mixed gas environment of a reducing gas and an inert gas, it is preferable to first place the starting material in a reducing gas environment or a mixed gas environment of a reducing gas and an inert gas. Heat treatment is performed at a temperature exceeding 600°C and less than 1000°C, and then, if necessary, heat treatment is performed at a temperature between 650°C and 1200°C in an inert gas atmosphere. The reducing gas at this time is not particularly limited, but is preferably H ₂ . Also, when using H ₂ as the reducing gas, as the composition of the reducing environment, H ₂ is preferably at least 0.1% by volume, and more preferably at least 1%. When H ₂ is at least 0.1% by volume, reduction can be efficiently performed.

From the viewpoint of improving weather resistance, it is preferable that the surface of the near-infrared-absorbing fine particles obtained in the above step is coated with an oxide containing one or more metals of Si, Ti, Zr, and Al. The coating method is not particularly limited, and the surface of the near-infrared shielding material particles can be coated by adding the above-mentioned metal alkoxide to the solution in which the near-infrared shielding material particles are dispersed.

3. Near-infrared curable ink composition

The near-infrared curable ink composition of the present invention can be obtained by adding uncured thermosetting resin after dispersing near-infrared absorbing fine particles in a suitable solvent. In addition, the near-infrared curable ink composition of the present invention can also be applied to the photoforming method of applying a predetermined amount and irradiating it with near-infrared rays to harden and deposit it, in addition to its conventional use as an ink. Shape three-dimensional objects.

There is no particular limitation on the method of dispersing the near-infrared absorbing fine particles in the solvent, but it is preferable to use a wet media mill.

Furthermore, for the near-infrared absorbing fine particles, the near-infrared absorbing fine particles may be dispersed together with a suitable dispersant in a suitable solvent.

Furthermore, if the dispersant is added for the purpose of dispersing the near-infrared-absorbing microparticles in the solvent, a suitable commercially available dispersant can be used, and the molecular structure of the dispersant preferably has a polyester-based, polyacrylic-based , polyurethane-based, polyamine-based, polycaprolactone-based, polystyrene-based main chains, and functional groups with amine groups, epoxy groups, carboxyl groups, Hydroxyl, sulfo, etc. This is because the dispersant having such a molecular structure does not deteriorate when the coating film of the near-infrared curable ink of the present invention is irradiated intermittently with near-infrared rays for tens of seconds.

Specific preferred examples of commercially available dispersants include SOLSPERSE 3000, SOLSPERSE 9000, SOLSPERSE 11200, SOLSPERSE 13000, SOLSPERSE 13240, SOLSPERSE 13650, SOLSPERSE 13940, SOLSPERSE 16000, SOLSPERSE 17000 manufactured by Japan Lubrizol Co., Ltd. , SOLSPERSE18000, SOLSPERSE20000, SOLSPERSE21000, SOLSPERSE24000SC, SOLSPERSE24000GR, SOLSPERSE26000, SOLSPERSE27000, SOLSPERSE28000, SOLSPERSE31845, SOLSPERSE32000, SOLSPERSE32500, SOLSPERSE32550, SOLSPERSE32600, SOLSPERSE33000, SOLSPERSE33500, SOLSPERSE34750, SOLSPERSE33500, SOLSPERSE34750 LSPERSE35100, SOLSPERSE35200, SOLSPERSE36600, SOLSPERSE37500, SOLSPERSE38500, SOLSPERSE39000, SOLSPERSE41000, SOLSPERSE41090, SOLSPERSE53095, SOLSPERSE55000, SOLSPERSE56000, SOLSP ERSE76500 etc.; BYK-Chemie Disperbyk-101, Disperbyk-103, Disperbyk-107, Disperbyk-108, Disperbyk-109, Disperbyk-110, Disperbyk-111, Disperbyk-112, Disperbyk-116, Disperbyk-130, Disperbyk-140 manufactured by Japan Co., Ltd. Disperbyk-142, Disperbyk-145, Disperbyk-154, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-165, Disperbyk-166, Disperbyk-167, Disperbyk-168, Disperbyk-170, Dis perbyk- 171, Disperbyk-174, Disperbyk-180, Disperbyk-181, Disperbyk-182, Disperbyk-183, Disperbyk-184, Disperbyk-185, Disperbyk-190, Disperbyk-2000, Disperbyk-2001, Disperbyk-2020, Disperbyk-2025, Disperbyk-2050, Disperbyk-2 070. Disperbyk- 2095, Disperbyk-2150, Disperbyk-2155, Anti-Terra-U, Anti-Terra-203, Anti-Terra-204, BYK-P104, BYK-P104S, BYK-220S, BYK-6919, etc.; BASF Japan (stock) EFKA4008, EFKA4046, EFKA4047, EFKA4015, EFKA4020, EFKA4050, EFKA4055, EFKA4060, EFKA4080, EFKA4300, EFKA4330, EFKA4400, EFKA4401, EFKA4402, EFKA4403 manufactured by the company , EFKA4500, EFKA4510, EFKA4530, EFKA4550, EFKA4560, EFKA4585, EFKA4800, EFKA5220, EFKA6230 , JONCRYL67, JONCRYL678, JONCRYL586, JONCRYL611, JONCRYL680, JONCRYL682, JONCRYL690, JONCRYL819, JONCRYL-JDX5050, etc.; 1. Ajisper PB-822, etc.

As a solvent for the near-infrared curable ink composition, for example, alcohols such as water, methanol, ethanol, propanol, butanol, isopropanol, isobutanol, and diacetone alcohol, ethers such as methyl ether, diethyl ether, and propyl ether can be used. Ketones, esters, acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone, isobutyl ketone and other ketones, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, polyethylene glycol, polypropylene glycol and other organic solvents.

Moreover, it is also preferable to use the monomer of the thermosetting resin in an uncured state together with or instead of the solvent of the near-infrared curable ink composition. In this case, as described below, a configuration not using a solvent such as an organic solvent can be employed.

Furthermore, it is also preferable to use a compound having 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 described later. Reactive organic solvents with functional groups are used as solvents for near-infrared curable ink compositions.

Examples of thermosetting resins include epoxy resins, urethane resins, acrylic resins, urea resins, melamine resins, phenol resins, ester resins, polyimide resins, silicone resins, and unsaturated polyester resins. resin etc. These thermosetting resins are cured by irradiating thermal energy to uncured thermosetting resins. In addition, the uncured thermosetting resin contains monomers or oligomers that form thermosetting resins through curing reactions, and known curing agents that are suitably added. Furthermore, a known hardening accelerator can also be added to the hardening agent.

The amount of the composite tungsten oxide as the near-infrared absorbing fine particles contained in the near-infrared curable ink of the present invention may be appropriately added in an amount that can be cured by the uncured thermosetting resin during the curing reaction. Therefore, it is only necessary to determine the amount of near-infrared-absorbing microparticles per unit area of the near-infrared-curable ink coated in consideration of the coating thickness of the near-infrared-curable ink.

As mentioned above, the following two cases are also preferable configurations: from a near-infrared curable ink composition containing a composite tungsten oxide as near-infrared-absorbing fine particles, and containing a solvent, a dispersant, and an uncured thermosetting resin A near-infrared curable ink composition is obtained by removing the solvent or without using a solvent, including a composite tungsten oxide as near-infrared absorbing fine particles, a dispersant, and an uncured thermosetting resin.

A near-infrared curable ink composition that does not contain a solvent but contains composite tungsten oxide as near-infrared-absorbing fine particles, a dispersant, and an uncured thermosetting resin The step of volatilizing the solvent can be omitted in the subsequent steps, and the efficiency of the hardening reaction is good.

The method for removing the solvent is not particularly limited, and a heating distillation method with reduced pressure operation, etc. can be used.

4. Near-infrared hardening film and light shaping method

The near-infrared curable film of the present invention is obtained by applying a predetermined amount of the obtained near-infrared curable ink composition of the present invention to obtain a coating film, and irradiating near-infrared rays to harden it. The principle is that the near-infrared absorbing particles absorb the irradiated near-infrared rays and generate heat, and the heat energy of this heat promotes the polymerization reaction or condensation reaction or addition of monomers or oligomers contained in the uncured thermosetting resin. reaction and other reactions, thereby causing the hardening reaction of the thermosetting resin. Moreover, the near-infrared rays absorbed by the irradiation of near-infrared rays generate heat generated by fine particles, and volatilization of the solvent also occurs.

On the other hand, even if near-infrared rays are further irradiated to the near-infrared cured film of the present invention, the cured film does not melt again. Since the near-infrared curable film of the present invention contains a thermosetting resin obtained by curing an uncured thermosetting resin, even if the near-infrared absorbing particles generate heat due to irradiation of near-infrared rays, they will not melt again.

This feature is particularly effective when applied to the following photolithography method, that is, a predetermined amount of the near-infrared curable ink composition of the present invention is cured and accumulated, and the application of the near-infrared curable ink and the application of the near-infrared curable ink are repeated. The layering of irradiation is repeated to create a three-dimensional object.

Of course, it is also preferable to obtain the near-infrared curable film of the present invention by applying a predetermined amount of the near-infrared curable ink composition of the present invention on a substrate and irradiating it with near-infrared rays to cure it.

The material of the substrate used in the present invention is not particularly limited, for example, paper, polyethylene terephthalate (PET, Polyethylene Terephthalate), acrylic acid, urethane, polyester, etc. can be preferably used for various purposes. Carbonate, polyethylene, ethylene-vinyl acetate copolymer, vinyl chloride, fluororesin, polyimide, polyacetal, polypropylene, nylon, etc. Moreover, glass can be preferably used other than paper and resin.

As a method for curing the near-infrared curable ink composition of the present invention, infrared radiation is preferred, and near-infrared radiation is more preferred. The energy density of near-infrared rays is relatively high, which can effectively give the resin in the ink composition the energy required for hardening.

It is also preferable to cure the near-infrared curable ink composition of the present invention by combining infrared irradiation with any method selected from known methods. For example, methods such as heating, air blowing, and irradiation of electromagnetic waves may be used in combination with infrared irradiation.

Furthermore, in the present invention, so-called infrared rays refer to electromagnetic waves having a wavelength in the range of 0.1 μm to 1 mm, so-called near infrared rays refer to infrared rays with a wavelength of 0.75 to 4 μm, and far infrared rays refer to infrared rays with a wavelength of 4 to 1000 μm. In general, the effects of the present invention can be obtained when any infrared rays called far infrared rays or near infrared rays are irradiated. In particular, when near-infrared rays are irradiated, the above-mentioned thermosetting resin can be efficiently cured in a shorter time.

Moreover, in this invention, a microwave means the electromagnetic wave which has the wavelength of the range of 1mm-1m.

The microwave to be irradiated preferably has a power of 200-1000W. If the power is more than 200W, the vaporization of the residual organic solvent in the ink will be promoted. If it is less than 1000W, the irradiation conditions will be softer, and there is no risk of deterioration of the base material or the above-mentioned thermosetting resin.

The preferred infrared irradiation time for the near-infrared-curable ink composition of the present invention varies according to the energy or wavelength of the irradiation, the composition of the near-infrared-curable ink, and the coating amount of the near-infrared-curable ink, but generally speaking, it is longer The irradiation time of 0.1 second or more is preferable. By setting the irradiation time to 0.1 second or more, infrared irradiation can be performed within the control range of the above-mentioned preferred power. The solvent in the ink composition can also be fully dried by prolonging the irradiation time, but if printing or coating at high speed is important, the irradiation time is preferably within 30 seconds, more preferably within 10 seconds.

As a source of infrared radiation, it can be obtained directly from a heat source, or effective infrared radiation can be obtained from it through a heat medium. For example, infrared rays can be obtained by mercury, xenon, cesium, sodium and other discharge lamps, or carbon dioxide gas lasers, and then heating resistors such as platinum, tungsten, nickel-chromium alloys, and Kantar. Furthermore, a halogen lamp is mentioned as a preferable radiation source. Halogen lamps have the advantages of good thermal efficiency and fast rise.

Irradiation of infrared rays to the near-infrared-curable ink composition of the present invention may be performed from the side on which the near-infrared-curable ink is applied, or may be performed from the back side. It is also preferable to simultaneously irradiate from both sides, and it is also preferable to combine it with elevated temperature drying or blast drying. Moreover, it is more preferable to use a light-condensing plate as needed. By combining these methods, it can be cured by short-term infrared irradiation.

The near-infrared-absorbing microparticles of the present invention have visible light transmittance, so a transparent infrared-shielding film can be easily obtained by curing them with infrared rays. Moreover, a colored film can be easily obtained by adding at least one or more kinds of various pigments or dyes. In this colored film, since there is almost no influence on the color tone caused by the near-infrared absorbing fine particles, it can be used for color filters of liquid crystal displays and the like.

As the pigment that can be used in the present invention in order to obtain the above-mentioned colored film, known pigments can be used without particular limitation, and insoluble pigments can be preferably used. Organic pigments such as pigments and lake pigments and inorganic pigments such as carbon black.

These pigments are preferably present in the state of being dispersed in the near-infrared curable ink composition of the present invention. As a method for dispersing such pigments, known methods can be used without particular limitation.

、

、噻

、二

、噻唑、酞菁、吡咯并吡咯二酮等。 As mentioned above, the insoluble pigment is not particularly limited, for example, azo, methine azo, methine, diphenylmethane, triphenylmethane, quinacridone, anthraquinone, perylene, indigo, quinophthalein Ketone, isoindolinone, isoindoline, acridine

,

, thiophene

,two

, thiazole, phthalocyanine, diketopyrrolopyrrole, etc.

As mentioned above, the pigment is not particularly limited, and the specific names of pigments that can be preferably used are listed below.

Examples of pigments for deep red or red include C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 48:1, C.I. Pigment Red 53:1, C.I. Pigment Red 57:1, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 139, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 202, C.I. Pigment Red 222, C.I. Pigment Violet 19, etc.

Examples of pigments for orange or yellow include C.I. Pigment Orange 31, C.I. Pigment Orange 43, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Yellow 17, C.I. Pigment Yellow 74, C.I. Pigment Yellow 93, C.I. Pigment Yellow 128, C.I. Pigment Yellow 94, C.I. Pigment Yellow 138, etc.

Examples of pigments for green or cyan include C.I. Pigment Blue 15, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 16, C.I. Pigment Blue 60, and C.I. Pigment Green 7.

Examples of pigments for black include C.I. Pigment Black 1, C.I. Pigment Black 6, C.I. Pigment Black 7, etc.

As mentioned above, the inorganic pigment is not particularly limited, and preferably includes carbon black, titanium dioxide, zinc sulfide, zinc oxide, zinc phosphate, mixed oxide metal phosphate, iron oxide, ferromanganese oxide, chromium oxide, ultramarine blue, nickel or Chromium antimony titanium oxide, cobalt oxide, aluminum, aluminum oxide, silicon oxide, silicate, zirconium oxide, mixed oxide of cobalt and aluminum, molybdenum sulfide, rutile mixed phase pigment, rare earth sulfide, bismuth vanadate , aluminum hydroxide or barium sulfate extender pigments, etc.

The average particle size of the dispersed pigment contained in the near-infrared curable ink composition of the present invention is preferably not less than 1 nm and not more than 200 nm. This is because the storage stability in the near-infrared curable ink composition is good when the average particle diameter of the pigment dispersion liquid is 1 nm to 200 nm.

As mentioned above, the dye used in the present invention is not particularly limited, and either oil-soluble dye or water-soluble dye can be used, and yellow dye, magenta dye, cyan dye, etc. can be preferably used.

As yellow dyes, there are, for example, aryl or heteroaryl azo dyes having phenols, naphthols, anilines, pyrazolones, pyridones, open-chain reactive methylene compounds as coupling components; For example, methine azo dyes with open-chain active methylene compounds as coupling components; such as methine dyes such as benzylidene dyes or monomethine oxazole dyes; such as naphthoquinone dyes, Quinophthalone dyes, nitro-nitroso dyes, acridine dyes, acridone dyes, etc. are exemplified as quinone-based dyes such as anthraquinone dyes and the like. These dyes can dissociate part of the chromophore to show yellow color. At this time, the counter cation can be an inorganic cation such as an alkali metal or ammonium, or an organic cation such as pyridinium or quaternary ammonium salt. , and furthermore, it may also be a polymer cation having these in a partial structure.

染料之類的碳陽離子染料；例如萘醌、蒽醌、蒽吡啶酮等之類的醌系染料；例如二

染料等之類的縮合多環系染料等。該等染料可為發色基之一部分進行解離才呈現深紅色者，此時之抗衡陽離子可為鹼金屬、或銨之類的無機陽離子，亦可為吡啶鎓、四級銨鹽之類的有機陽離子，進而亦可為部分構造中具有該等之聚合物陽離子。 Examples of deep red dyes include aryl or heteroaryl azo dyes having phenols, naphthols, and anilines as coupling components; Methylene azo dyes; methine dyes such as arylene dyes, styryl dyes, merocyanine dyes, oxonol dyes; diphenylmethane dyes, triphenylmethane dyes,

Carbocation dyes such as dyes; quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc.; such as di

Condensed polycyclic dyes such as dyes and the like. These dyes can be part of the chromophore to dissociate to show deep red. At this time, the counter cation can be an inorganic cation such as an alkali metal or ammonium, or an organic cation such as pyridinium or quaternary ammonium salt. Cations, and further, polymer cations having them in a partial structure may also be used.

染料之類的碳陽離子染料；酞菁染料；蒽醌染料；例如具有酚類、萘酚類、苯胺類作為偶合成分之芳基或雜芳基偶氮染料；靛藍-硫代靛藍染料。該等染料可為發色基之一部分進行解離才呈現青色者，此時之抗衡陽離子可為鹼金屬、或銨之類的無機陽離子，亦可為吡啶鎓、四級銨鹽之類的有機陽離子，進而亦可為部分構造中具有該等之聚合物陽離子。又，亦可使用多偶氮染料等黑色染料。 Examples of cyan dyes include methine azo dyes such as indoaniline dyes and indophenol dyes; polymethine dyes such as cyanine dyes, oxonol dyes, and merocyanine dyes; diphenylmethane dyes, triphenylmethane dye,

Carbocationic dyes such as dyes; phthalocyanine dyes; anthraquinone dyes; aryl or heteroaryl azo dyes having, for example, phenols, naphthols, anilines as coupling components; indigo-thioindigo dyes. These dyes can display a cyan color by dissociation of a part of the chromophore. At this time, the counter cation can be an inorganic cation such as an alkali metal or ammonium, or an organic cation such as pyridinium or quaternary ammonium salt. , and furthermore, it may also be a polymer cation having these in a partial structure. Moreover, black dyes, such as a polyazo dye, can also be used.

As mentioned above, the water-soluble dye used in the present invention is not particularly limited, and direct dyes, acid dyes, food dyes, basic dyes, reactive dyes and the like can be preferably used.

Specific dye names that can be preferably used are listed below as water-soluble dyes.

Examples include C.I. Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184 , 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, C.I. Direct Violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, C.I. Direct Yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59 , 68, 86, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 132, 142, 144, 161, 163, C.I. Direct Blue 1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 151, 156, 158, 159, 160, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237, 244, 248, 249, 251, 252, 264, 270, 280, 288, 289, 291, C.I. Direct Black 9, 17, 19, 22, 32, 51, 56, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 114, 117, 118, 121, 122, 125 , 132, 146, 154, 166, 168, 173, 199, C.I. Acid Red 35, 42, 52, 5, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 154, 158, 249, 254, 257, 261, 263, 266, 289, 299, 301, 305, 336, 337, 361, 396, 397, C.I. 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. Acid Blue 9, 25, 40, 41, 62, 72, 76, 78, 80, 82, 92, 106, 112, 113, 120, 127: 1, 129, 138, 143, 175, 181, 205, 207 , 220, 221, 230, 232, 247, 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326, C.I. Acid Black 7, 24, 29, 48, 52: 1, 172, C.I. Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55, C.I. Reactive Violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34, C.I. Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, C.I. Reactive Blue 2, 3, 5, 8, 10, 13, 14, 15, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38, C.I. Reactive Black 4, 5, 8, 14, 21, 23, 26, 31, 32, 34, C.I. Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46, C.I. Basic Violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48, C.I. Basic Yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40, C.I. Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71, C.I. Basic Black 8, etc.

Coloring materials contained in the near-infrared hardening ink described above The particle size of the pigment or the near-infrared-absorbing fine particles is preferably determined in consideration of the characteristics of the coating device for the near-infrared curable ink.

[Example]

Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to these.

(Example 1)

Predetermined amounts of powders of tungstic acid and cesium carbonate described as H ₂ WO ₄ were weighed so that the molar ratio of W and Cs was 1:0.33, and the two powders were mixed. This mixed powder was used as a starting material. Cs _0.33 WO was prepared by heating the starting material at 600°C for 1 hour in a reducing environment (nitrogen/hydrogen=97/3 (volume ratio)), and replacing it with an argon atmosphere at 800°C for 1 hour. ₃ powder. The powder had a specific surface area of 20 m ² /g. Also, the identification result of the crystal phase by X-ray diffraction is single-phase hexagonal tungsten bronze (composite tungsten oxide particles).

ZrO₂珠粒之塗料振盪機中，進行6小時分散處理，製成分散粒徑80nm之Cs_0.33WO₃分散液(A液)。將該A液25重量份、與市售之單液型且包含未硬化之熱硬化性樹脂的熱硬化型油墨(帝國油墨製造公司製造，MEG絲印油墨(介質))75重量份進行混合，而製備實施例1之近紅外線硬化型油墨。 20 parts by weight of this Cs _0.33 WO ₃ powder, 65 parts by weight of methyl isobutyl ketone, and 15 parts by weight of an acrylic dispersant were mixed. Fill them to 0.3mm

In the coating shaker of ZrO ₂ beads, carry out the dispersion treatment for 6 hours, and make the Cs _0.33 WO ₃ dispersion liquid (A liquid) with a dispersed particle diameter of 80nm. 25 parts by weight of this liquid A was mixed with 75 parts by weight of a commercially available one-component type thermosetting ink (manufactured by Imperial Ink Manufacturing Co., Ltd., MEG screen printing ink (medium)) containing an uncured thermosetting resin, and The near-infrared curing ink of Example 1 was prepared.

Coat the near-infrared curable ink on glass with a bar coater (No. 10), and install a line heater HYP-14N (output 980W) manufactured by HIVEC Co., Ltd. at a height of 5 cm from the coating surface As the irradiation source of near-infrared rays, irradiate near-infrared rays for 10 seconds to obtain a cured film.

It was confirmed that the obtained cured film was transparent visually.

The adhesiveness of the obtained cured film was evaluated by the method shown below.

Make 100 square-shaped cuts using a tool guide with a gap interval of 1 mm, and attach an 18-mm-width adhesive tape (Sellotape (registered trademark) CT-18 manufactured by Miqibang Co., Ltd.) to the square-shaped cuts Use a 2.0kg roller to reciprocate 20 times to make the surface completely adhered, then peel it off rapidly at a peeling angle of 180 degrees, and count the number of squares peeled off.

The number of squares peeled off is 0.

Even if the obtained cured film was irradiated with near-infrared rays under the same conditions as when the above-mentioned near-infrared curable ink was cured for 20 seconds, the cured film did not melt again.

(Example 2)

In Example 1, the cured film of Example 2 was obtained by performing the same operation as Example 1 except mixing 30 parts by weight of A liquid and 70 parts by weight of commercially available single-component thermosetting ink.

The method similar to Example 1 evaluated the adhesiveness of the obtained cured film of Example 2.

The adhesion between the cured film of Example 2 and the glass substrate was good, and the number of squares peeled off was zero.

(Example 3)

In Example 1, except that 35 parts by weight of A liquid was mixed with 65 parts by weight of commercially available single-component thermosetting ink, the same operation as in Example 1 was carried out. The near-infrared cured film of Example 3 was obtained.

The method similar to Example 1 evaluated the adhesiveness of the obtained cured film of Example 3.

The adhesion between the cured film and the glass substrate of Example 3 was good, and the number of peeled squares was zero.

(Example 4)

Except that the near-infrared curable ink of Example 1 is coated on high-quality paper (manufactured by Nippon Paper, npi high-quality) with a basis weight of 81.4g/m ² , the same operation as in Example 1 is carried out to obtain the hardened ink of Example 4. membrane. The state of the cured film coated on the obtained high-quality paper was evaluated as follows.

(Evaluation of hardened film coated on high-quality paper)

Overlay unprinted high-quality paper on the hardened film just after production, and rub it with a bamboo brush from the top, and evaluate the adhesion state of the ink from the sample to the overlapped paper.

Among them, ○: No ink adhesion to the overlapped paper surface.

△: Adhesion of ink can be seen on more than 1% of the overlapped paper surface.

×: Adhesion of ink can be seen on 3% or more of the overlapped paper surface.

As a result, the evaluation result of the cured film of Example 4 was ◯.

(Example 5)

ZrO₂珠粒之塗料振盪機進行4小時分散處理，而製備分散粒徑150nm之Cs_0.33WO₃分散液(B液)。 It is the same as liquid A in Example 1, but the 0.3mm

The coating shaker of ZrO ₂ beads was dispersed for 4 hours to prepare a Cs _0.33 WO ₃ dispersion (liquid B) with a dispersed particle diameter of 150 nm.

Except having used this B liquid instead of A liquid, the operation similar to Example 1 was performed, and the cured film of Example 5 was obtained.

It was confirmed that the obtained cured film was transparent visually.

The method similar to Example 1 evaluated the adhesiveness of the obtained cured film of Example 5.

The adhesion between the cured film and the glass substrate of Example 5 was good, and the number of squares peeled off was zero.

(Example 6)

ZrO₂珠粒之塗料振盪機進行2小時分散處理，而製備分散粒徑800nm之Cs_0.33WO₃分散液(C液)。 It is the same as liquid A in Example 1, but the 0.3mm

The coating shaker of ZrO ₂ beads was dispersed for 2 hours to prepare a Cs _0.33 WO ₃ dispersion (Liquid C) with a dispersed particle diameter of 800 nm.

Except having used this C liquid instead of A liquid, the operation similar to Example 1 was performed, and the cured film of Example 6 was obtained.

It was confirmed that the obtained cured film was transparent visually.

The method similar to Example 1 evaluated the adhesiveness of the obtained cured film of Example 6.

In the cured film of Example 6, the number of squares peeled off was 24.

(Example 7)

ZrO₂珠粒之塗料振盪機進行10小時分散處理，而製備分散粒徑20nm之Cs_0.33WO₃分散液(D液)。 It is the same as liquid A in Example 1, but the 0.3mm

The coating shaker of ZrO ₂ beads was dispersed for 10 hours to prepare a Cs _0.33 WO ₃ dispersion (liquid D) with a particle size of 20 nm.

Except using this D liquid instead of A liquid, carry out the operation identical with embodiment 1 and The cured film of Example 7 was obtained.

It was confirmed that the obtained cured film was transparent visually.

The method similar to Example 1 evaluated the adhesiveness of the obtained cured film of Example 7.

In the cured film of Example 7, the number of squares peeled off was zero.

(Embodiment 8)

In the same manner as in Example 1, except that 25 parts by weight of liquid A in Example 1, 37.5 parts by weight of uncured bisphenol A epoxy resin, and 37.5 parts by weight of a hardener added with a hardening accelerator were mixed The near-infrared curing ink of Example 8 was prepared. Furthermore, the hardener is a mixture of phenol resin and imidazole.

Except having used the near-infrared curable ink of Example 8, the same operation as Example 1 was performed, and the cured film of Example 8 was obtained.

The method similar to Example 1 evaluated the adhesiveness of the obtained cured film of Example 8.

In the cured film of Example 8, the number of squares peeled off was zero.

(Example 9)

Except mixing 30 parts by weight of liquid A of Example 1, 35 parts by weight of uncured bisphenol A type epoxy resin, and 35 parts by weight of a curing agent added with a hardening accelerator, in the same manner as in Example 1 The near-infrared curing ink of Example 9 was prepared. Furthermore, the hardener is a mixture of phenol resin and imidazole.

Except having used the near-infrared curable ink of Example 9, the same operation as Example 1 was performed, and the cured film of Example 9 was obtained.

The method similar to Example 1 evaluated the adhesiveness of the obtained cured film of Example 9.

The adhesiveness of the cured film of Example 9 and the glass substrate was good, and the number of squares peeled off was 0.

(Example 10)

Except mixing 35 parts by weight of liquid A of Example 1, 32.5 parts by weight of uncured bisphenol A type epoxy resin, and 32.5 parts by weight of hardening agent added with a hardening accelerator, in the same manner as in Example 1 The near-infrared curable ink of Example 10 was prepared. Furthermore, the hardener is a mixture of phenol resin and imidazole.

Except having used the near-infrared curable ink of Example 10, the same operation as Example 1 was performed, and the cured film of Example 10 was obtained.

The method similar to Example 1 evaluated the adhesiveness of the obtained cured film of Example 10.

The adhesion between the cured film and the glass substrate of Example 10 was good, and the number of squares peeled off was zero.

(Example 11)

Except that the near-infrared curable ink of embodiment 8 is coated on the high-quality paper (manufactured by Nippon Paper, npi high-quality) with a basis weight of 81.4g/ ^m2 , the same operation as in embodiment 1 is carried out to obtain the cured ink of embodiment 11 membrane. The state of the cured film coated on the obtained high-quality paper was evaluated in the same manner as in Example 4.

As a result, the evaluation result of the cured film of Example 11 was ◯.

(comparative example 1)

A liquid (E liquid) in which 65 parts by weight of methyl isobutyl ketone and 15 parts by weight of an acrylic dispersant were mixed was prepared.

Except having used this E liquid instead of A liquid, the operation similar to Example 1 was performed, and the cured film of the comparative example 1 was obtained.

However, the film was not cured at all, and a cured film could not be obtained.

(comparative example 2)

Except having used phthalocyanine powder instead of Cs _0.33 WO ₃ powder, the same operation as Example 1 was performed, and the cured film of the comparative example 2 was obtained.

The method similar to Example 1 was going to evaluate the adhesiveness of the obtained cured film of the comparative example 2.

The hardening of the cured film of the comparative example 2 was insufficient, and the adhesiveness evaluation was not possible.

(comparative example 3)

Except having used the E liquid of the comparative example 1 instead of the A liquid, the same operation as Example 4 was performed, and the cured film of the comparative example 3 was obtained.

The cured film of Comparative Example 3 coated on high-quality paper was evaluated in the same manner as in Example 4. As a result, the evaluation result of the cured film of Comparative Example 3 was x.

(comparative example 4)

In addition to using 75 parts by weight of a styrene solution obtained by dissolving 40 parts by weight of a styrene resin as a thermoplastic resin in 60 parts by weight of methyl ethyl ketone instead of a commercially available one-component type containing an uncured thermosetting resin Thermosetting ink (Imperial Ink Manufacturing Co. Production, MEG screen printing ink (medium)) 75 parts by weight, performed the same operation as Example 1, and obtained the cured film of Comparative Example 4.

When the obtained cured film was irradiated with near-infrared rays under the same conditions as when the above-mentioned near-infrared curable ink was cured for 20 seconds, the cured film was softened. Since this softening was confirmed, other evaluations were canceled.

(comparative example 5)

Except for using liquid E of comparative example 1 instead of liquid A, the cured film of comparative example 5 was obtained by performing the same operation as that of example 8.

However, the film was not cured at all, and a cured film could not be obtained.

(comparative example 6)

The cured film of Comparative Example 6 was obtained by performing the same operation as in Example 11 except that Liquid E of Comparative Example 1 was used instead of Liquid A. The state of the cured film coated on the obtained high-quality paper was evaluated in the same manner as in Example 4.

As a result, the evaluation result of the cured film of Comparative Example 6 was x.

Claims (6)

A near-infrared curable composition for ink printing, characterized in that it includes composite tungsten oxide as near-infrared absorbing particles, uncured thermosetting resin, solvent, acrylic dispersant, and hardener; the composite tungsten The oxide is a single-phase hexagonal crystal Cs _x W _y O _z (0.001≦x/y≦1, 2.2≦z/y≦3.0); the dispersed particle size of the above-mentioned near-infrared absorbing particles is 1nm or more and 50nm or less; the above-mentioned solvent At least one selected from the group consisting of water, alcohols, ethers, esters, ketones, monomers of thermosetting resins in an uncured state, and reactive organic solvents having epoxy groups. The near-infrared curable composition for ink printing according to claim 1, wherein the acrylic dispersant has a functional group selected from the group consisting of amine group, epoxy group, carboxyl group, hydroxyl group, and sulfo group. The near-infrared curable composition for ink printing according to claim 1 or 2, wherein the surface of the near-infrared absorbing fine particles is coated with an oxide containing any one or more of Si, Ti, Zr, and Al. The near-infrared curable composition for ink printing according to claim 1 or 2, further comprising any one or more selected from organic pigments, inorganic pigments, and dyes. A near-infrared curable film, characterized in that it is a near-infrared curable composition for ink printing according to any one of claims 1 to 4, which is cured by near-infrared radiation. A light shaping method, characterized in that: coating the near-infrared hardening type composition for ink printing according to any one of claims 1 to 4 to form a coating, and irradiating near-infrared rays to the coating to make It hardens.