TW201934494A - Near-infrared curable ink composition, near infrared cured film, and production method thereof, and optical shaping method - Google Patents

Abstract

Provided are: a near infrared radiation curable ink composition containing composite tungsten oxide fine particles which have sufficient near infrared absorptivity and excellent adhesion to a substrate; a near infrared radiation cured film; and a stereolithography method using the near infrared radiation curable ink composition. Provided are: a near infrared radiation cured film using a near infrared radiation curable ink composition which comprises an uncured thermosetting resin and a composite tungsten oxide having near infrared absorptivity, wherein the composite tungsten oxide includes a hexagonal crystal structure, has an a-axis lattice constant of 7.3850-7.4186 Å and a c-axis lattice constant of 7.5600-7.6240 Å, and has an average particle size of 100 nm or less; and a stereolithography method using the near infrared radiation curable ink composition.

Description

Near-infrared hardening type ink composition, near-infrared hardening film, and manufacturing method and photoforming method thereof

The present invention relates to a manufacturing method and photoforming method of a near-infrared hardening type ink composition, a near-infrared hardening film, and the like.

UV-curable coatings that cure with ultraviolet light can be printed without heating. Therefore, in recent years, it has been widely known as an environmentally-friendly paint. For example, there have been proposals or disclosures described in Patent Documents 1 to 6.

However, according to the review by the inventors of the present application, as a UV-curable ink or coating, when a composition that undergoes radical polymerization by ultraviolet irradiation is used, polymerization (hardening) is hindered if oxygen is present. On the other hand, when using a composition that undergoes cationic polymerization by ultraviolet irradiation, there is a problem that a strong acid is generated during the polymerization.

Moreover, in order to improve the light resistance of a printing surface or a coating surface, an ultraviolet absorber is generally added to this printing surface or a coating surface. However, when a UV absorbent is added to a UV-curable ink or paint, there is a problem that the curing by UV irradiation is hindered.

In order to solve the above-mentioned problems, Patent Documents 7 and 8 propose a near-infrared curing composition that does not use ultraviolet rays and is cured by irradiation with near-infrared rays.

In addition, the applicant of the present application disclosed in Patent Document 9 a near-infrared hardening type ink composition containing a composite tungsten oxide.

[Prior technical literature] [Patent Literature]

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

[Patent Document 2] Japanese Patent No. 3354122

[Patent Document 3] Japanese Patent No. 5267854

[Patent Document 4] Japanese Patent No. 5626648

[Patent Document 5] 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

[Patent Document 9] International Patent Publication No. 2017/047736

However, according to a further review by the inventors of the present case, the near-infrared hardening composition described in Patent Documents 7 and 8 has a problem of insufficient near-infrared absorption characteristics.

On the other hand, the market is increasingly demanding near-infrared curable compositions. For example, even if it is a near-infrared hardening type ink composition or a near-infrared hardening film containing a composite tungsten oxide described in Patent Document 9, it is considered that it will be difficult to continue to meet the market demand for improving the adhesion of the substrate.

This invention is completed based on the above situation, and the lesson it wants to solve The problem is to provide a near-infrared-curable ink composition which is provided on a predetermined substrate and irradiated with near-infrared light to harden it. A near-infrared hardening film, a method for manufacturing the same, and a photoforming method using the near-infrared hardening ink composition.

In order to solve the above-mentioned problems, the inventors of the present case conducted research, and it was considered effective to improve the near-infrared absorption capacity of the composite tungsten oxide fine particles, and to increase the heat generation amount when the near-infrared hardening ink composition was irradiated with near-infrared. Then, by increasing the calorific value, the hardening degree of the ink composition is increased, and the adhesion to the substrate is improved.

That is, the first invention for solving the above-mentioned problem is a near-infrared hardening type ink composition, which is composed of composite tungsten oxide fine particles having near-infrared absorption ability and an unhardened thermosetting resin; The composite tungsten oxide fine particles are composite tungsten oxide fine particles containing a hexagonal crystal structure; the lattice constants of the composite tungsten oxide fine particles are a-axis of 7.3850Å or more and 7.4186Å or less, and a c-axis of 7.5600Å or more and 7.6240. Å or less; the average particle diameter of the composite tungsten oxide fine particles is 100 nm or less.

The second invention is the near-infrared hardening ink composition of the first invention, wherein the lattice constant of the composite tungsten oxide fine particles is a-axis of 7.4031 Å or more and 7.4111 Å or less, and a c-axis of 7.5891 Å or more and 7.6240 Å or less. .

The third invention is the near-infrared curable ink composition of the first or second invention, wherein the average particle diameter of the composite tungsten oxide fine particles is 10 nm or more and 100 nm or less.

The fourth invention is the near-infrared hardening ink composition according to any one of the first to third inventions, wherein the composite tungsten oxide fine particles have a crystal grain diameter of 10 nm or more and 100 nm or less.

The fifth invention is the near-infrared curable ink composition according to any one of the first to fourth inventions, which further contains a dispersant.

The sixth invention is the near-infrared curable ink composition according to any one of the first to fifth inventions, and further contains a solvent.

The seventh invention is the near-infrared curable ink composition according to any one of the first to sixth inventions, wherein the composite tungsten oxide is of the general formula M _x W _y O _z (wherein the element M is selected from H and 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 of Yb, W is tungsten, O is oxygen, and 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0).

The eighth invention is a near-infrared hardening ink composition according to the seventh invention, wherein the composite tungsten oxide is composed of a composite tungsten oxide whose M element is one or more selected from Cs and Rb.

The ninth invention is the near-infrared hardening ink composition according to any one of the first to eighth inventions, wherein at least a part of the surface of the composite tungsten oxide fine particles is made of a material containing at least one selected from Si, Ti, Zr, and Al. The surface is covered with a film of at least one element.

A tenth invention is a near-infrared curable ink composition according to the ninth invention, wherein the surface coating film contains an oxygen atom.

The eleventh invention is the near-infrared curable ink composition according to any one of the first to tenth inventions, which further contains any one or more selected from the group consisting of organic pigments, inorganic pigments, and dyes.

A twelfth invention is a near-infrared hardened film, which is obtained by subjecting the near-infrared hardening ink composition according to any one of the first to eleventh inventions to near-infrared radiation and curing.

The thirteenth invention is a photoforming method, wherein the near-infrared curable ink composition according to any one of the first to eleventh inventions is applied to a substrate to form a coating material, and the coating material is irradiated with the coating material. Infrared hardens it.

The fourteenth invention is a method for manufacturing a near-infrared hardening ink composition, which is a near-infrared hardening ink composition containing near-infrared absorbing composite tungsten oxide particles, an unhardened thermosetting resin, a dispersant, and a solvent. The manufacturing method is characterized in that the composite tungsten oxide fine particles are composite tungsten oxide fine particles containing a crystalline structure of hexagonal crystals; and the composite tungsten oxide fine particles are based on a lattice constant of an a-axis of 7.3850Å or more and 7.4186Å. Hereinafter, the c-axis is manufactured in a range of 7.5600 Å or more and 7.6240 Å or less; while the range of the lattice constant of the composite tungsten oxide fine particles is maintained, a crushing and dispersion process step is performed so that the average particle diameter is 100 nm or less. .

The fifteenth invention is the method for producing a near-infrared hardening ink composition according to the fourteenth invention, wherein the composite tungsten oxide is of the general formula M _x W _y O _z (wherein 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, Yb More than one element, W is tungsten, O is oxygen, and 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0).

A sixteenth invention is the method for producing a near-infrared hardening ink composition according to the fourteenth or fifteenth invention, wherein the composite tungsten oxide is composed of a composite tungsten oxide whose M element is one or more selected from Cs and Rb. .

A seventeenth invention is the method for producing a near-infrared hardening ink composition according to any one of the fourteenth to sixteenth inventions, wherein at least a part of the surface of the composite tungsten oxide fine particles is composed of Si, Ti, Zr, Al The surface of any one or more elements is covered with a film.

An eighteenth invention is a method for producing a near-infrared curable ink composition according to the seventeenth invention, wherein the surface coating film contains an oxygen atom.

The 19th invention is the method for producing a near-infrared curable ink composition according to any one of the 14th to 18th inventions, wherein the near-infrared curable ink composition further contains any one selected from the group consisting of organic pigments, inorganic pigments, and dyes. More than that.

The near-infrared hardening type ink composition of the present invention is excellent in adhesion to a substrate and is industrially useful.

1‧‧‧thermoplasma

2‧‧‧ high frequency coil

3‧‧‧ sheath flow gas supply nozzle

4‧‧‧ Plasma gas supply nozzle

5‧‧‧ raw material powder supply nozzle

6‧‧‧ reaction container

7‧‧‧ suction tube

8‧‧‧ Filter

FIG. 1 is a conceptual diagram of one embodiment of a high-frequency thermoplasma reaction device used in the production of the composite tungsten oxide fine particles of the present invention.

In the following, the near-infrared curable ink of the present invention and the light forming method using the same are described in detail in order [1] a near-infrared hardening ink composition, [2] a near-infrared hardening film, and a light forming method.

[1] Near-infrared curing ink composition

The near-infrared hardening type ink composition of the present invention contains composite tungsten oxide fine particles having near-infrared absorbing ability, unhardened thermosetting resin, and other components as needed. Therefore, [a] composite tungsten oxide fine particles, [b] composite tungsten oxide fine particles, [c] uncured thermosetting resin, [d] other components, and [e] near-infrared hardening are explained in order below. Type ink composition.

[a] Composite tungsten oxide particles

The near-infrared absorbing fine particles used as the near-infrared hardening ink composition are composite tungsten oxide fine particles, and carbon black powder or tin-added indium oxide (hereinafter sometimes referred to as "ITO") powder are considered. However, if a carbon black powder is used as the near-infrared absorbing fine particles, since the powder is black, the degree of freedom in color selection of the near-infrared curable ink composition is reduced. On the other hand, when an ITO powder is used as the near-infrared absorbing fine particles, the hardenability of the near-infrared-curable ink composition cannot be exhibited unless the powder is added in a large amount. Therefore, if the ITO powder is added in a large amount, the powder is added in a large amount, which causes a problem that affects the color tone of the near-infrared curing ink composition.

In the near-infrared hardened film containing near-infrared absorbing fine particles, since the coloring of the near-infrared absorbing fine particles is not good, in the present invention, it is considered to contain composite tungsten oxide fine particles that do not cause coloring due to the fine particles as near Infrared absorbing particles.

By forming the composite tungsten oxide fine particles into near-infrared absorbing fine particles, free electrons are generated in the composite tungsten oxide fine particles, and the absorption characteristics from free electrons are exhibited in the near-infrared region. As a result, the composite tungsten oxide fine particles can be effectively used as near-infrared absorbing fine particles in the vicinity of a wavelength of 1000 nm.

The composite tungsten oxide fine particles of the present invention have near-infrared absorption characteristics, and are composite tungsten oxide fine particles having a crystal structure containing hexagonal crystals. The lattice constant system is 7.3850Å or more and 7.4186Å or less, and 7.5600Å or more is the c axis And those below 7.6240Å.

In the composite tungsten oxide fine particles of the present invention, the value of [c-axis lattice constant / a-axis lattice constant] is preferably 1.0221 or more and 1.0289 or less.

For the composite tungsten oxide fine particles of the present invention, (1) the crystal structure and the lattice constant, (2) the particle diameter and grain diameter, (3) the composition of the composite tungsten oxide fine particles, and (4) the composite tungsten The surface coating of the oxide fine particles is summarized in (5).

(1) Crystal structure and lattice constant

In addition to the hexagonal crystal, the composite tungsten oxide fine particles of the present invention can be formed into a structure of tetragonal or cubic tungsten bronze, and can be effectively used as a near-infrared absorbing material when formed into any structure. However, depending on the crystal structure formed by the composite tungsten oxide fine particles, the absorption position in the near-infrared region tends to be changed. That is, the absorption position in the near-infrared region tends to move to a longer wavelength side than a cubic crystal during a tetragonal crystal, and move to a longer wavelength side than a cubic crystal during a hexagonal crystal. In addition, with the change of the absorption position, the light absorption in the visible light region is the least hexagonal crystal, followed by the cubic crystal, and the cubic crystal is the largest one.

Based on the above findings, for the purpose of making the light in the visible region more transparent and absorbing the light in the near-infrared region, it is best to use hexagonal tungsten bronze. In the case where the composite tungsten oxide fine particles have a hexagonal crystal crystalline structure, the visible light region of the fine particles has a higher penetration and a near-infrared region has a higher absorption. In the crystal structure of the hexagonal crystal, a hexagonal void (channel) is formed by 6 sets of an 8-sided system formed by WO ₆ units, and M elements are arranged in the void to form a unit, and a number of this unit are collected The hexagonal crystal structure is formed.

In order to obtain the effect of improving the penetration in the visible light region and the absorption in the near-infrared region, if the composite tungsten oxide particles contain a unit structure (a set of 6 octahedrons formed according to WO ₆ units is formed into a hexagon) And a structure in which the M element is arranged in the gap).

When a cation containing M element is added to the hexagonal void, the absorption in the near-infrared region is enhanced. Here, in general, the hexagonal crystal is formed when the M element with a larger ionic radius is added, and specifically, it is easier to form the hexagonal crystal when one or more selected from Cs, Rb, K, Tl, Ba, and In are added. It is better.

Furthermore, the M element with a large plasma radius is added with one or more types of composite tungsten oxide particles selected from Cs and Rb, which can achieve absorption in the near-infrared region and penetration in the visible region.

Furthermore, when two or more elements are selected as the M element, one of them is selected from Cs, Rb, K, Tl, Ba, and In, and the remaining is selected from one or more elements constituting the M element, and sometimes it becomes a hexagonal crystal. .

When Cs tungsten oxide fine particles with Cs as the M element are selected, their lattice constants are preferably a-axis of 7.4031 Å or more and 7.4186 Å or less, and c-axis of 7.5750 Å or more and 7.6240 Å or less; the a-axis is preferably Above 7.4031Å and 7.4111Å Below, the c-axis is 7.5891Å to 7.6240Å.

When Rb tungsten oxide fine particles having Rb as the M element are selected, the lattice constants thereof are preferably 7.3850 Å or more and 7.3950 Å or less, and 7.5600 Å or more and 7.5700 Å or less on the c axis.

When CsRb tungsten oxide fine particles with Cs and Rb as the M elements are selected, the lattice constants thereof are preferably 7.3850 Å or more and 7.4186 Å or less, and 7.5600 Å or more and 7.6240 Å or less on the c axis.

However, the M element is not limited to the above-mentioned Cs or Rb. Even if the M element is an element other than Cs or Rb, it may suffice if the M element is present in a hexagonal void formed by WO ₆ units.

When the composite tungsten oxide having a hexagonal crystal structure according to the present invention is represented by the general formula M _x W _y O _z , when the composite tungsten oxide fine particles have a uniform crystal structure, the addition amount of the M element is 0.001. ≦ x / y ≦ 1, preferably 0.2 ≦ x / y ≦ 0.5, more preferably 0.20 ≦ x / y ≦ 0.37, and most preferably x / y = 0.33. The reason can be considered that when z / y = 3 and x / y = 0.33, the M element is added to all the voids in the hexagon. Typical examples include Cs _0.33 WO ₃ , Cs _0.03 Rb _0.30 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO ₃ and the like.

Here, the inventors of this case have repeatedly studied the countermeasures for further improving the near-infrared absorption function of the composite tungsten oxide fine particles, and considered a configuration that further increases the amount of free electrons contained.

That is, as a countermeasure for increasing the amount of free electrons, it is considered that a mechanical treatment is applied to the composite tungsten oxide fine particles, and appropriate strain or deformation is imparted to the hexagonal crystals contained therein. It is considered that in the hexagonal crystal to which appropriate strain or deformation is imparted, the overlapping state of the electron orbitals of the atoms constituting the grain structure is changed, and the amount of free electrons is increased.

Based on the above thoughts, the inventors of the present invention produced composite tungsten oxide fine particle dispersion liquids with respect to the particles of the composite tungsten oxide produced in the firing step of the "synthesis method of [b] composite tungsten oxide fine particles" described later. In the dispersing step, the particles of the composite tungsten oxide are pulverized under predetermined conditions, thereby straining or deforming the crystal structure, increasing the amount of free electrons, and further improving the near-infrared absorption function of the composite tungsten oxide particles. the study.

Then, based on the research, the particles of the composite tungsten oxide generated through the firing step were reviewed with a focus on each particle. As a result, it was found that the lattice constant and the composition of the constituent elements were deviated from each other.

After further research, it was found that even if the lattice constants or the composition of the constituent elements of the particles are different, the composite tungsten oxide fine particles finally obtained, if the lattice constants are within a predetermined range, exhibit the required optical properties. characteristic.

The inventors who have learned the above findings further measured the a-axis and c-axis of the crystal structure of the composite tungsten oxide microparticles that belong to the lattice constant, thereby grasping the degree of strain or deformation of the crystal structure of the microparticles. The exerted optical characteristics were studied.

Then, according to the results of the study, it is known that in the hexagonal composite tungsten oxide fine particles, when the a-axis is 7.3850Å or more and 7.4186Å or less, and the c-axis is 7.5600Å or more and 7.6240Å or less, the microparticle system is shown in The wavelength range of 350nm ~ 600nm has a maximum value, and the wavelength range of 800nm ~ 2100nm has a minimum value of light transmittance. It belongs to the composite tungsten oxide fine particles that can exert excellent near infrared absorption effect.

Furthermore, in the hexagonal composite tungsten oxide fine particles having the composite tungsten oxide fine particles of the present invention having an a-axis of 7.3850Å or more and 7.4186Å or less and a c-axis of 7.5600Å or more and 7.6240Å or less, the element M is represented. X / y When the value is in the range of 0.001 ≦ x / y ≦ 1, and preferably in the range of 0.20 ≦ x / y ≦ 0.37, a particularly excellent near-infrared absorption effect is exhibited.

In addition, it was also found that the composite tungsten oxide fine particles are preferably single crystals having a volume ratio of an amorphous phase of 50% or less.

It can be considered that if the volume ratio of the composite tungsten oxide fine particle-based amorphous phase is 50% or less of a single crystal, the crystal lattice diameter can be maintained at 10 nm or more and 100 nm or less while maintaining the lattice constant below the predetermined range. Can exert excellent optical characteristics.

In addition, when the composite tungsten oxide fine particles are single crystals, they are in an electron microscope image such as a transmission electron microscope. Since no grain boundaries are observed inside each fine particle, only the same lattice pattern is observed. confirm. In the case where the volume ratio of the amorphous phase in the composite tungsten oxide fine particles is 50% or less, it is also similar to the transmission electron microscope image, and the same grid pattern can be observed due to the entire particles, and almost no It was confirmed that an obscure pattern was observed.

In addition, since an amorphous phase is mostly present in the outer peripheral portion of each fine particle, by focusing on the outer peripheral portion of each fine particle, the volume ratio of the amorphous phase can be calculated in many cases. For example, in the case of true-spherical composite tungsten oxide fine particles, in the case where an amorphous phase in which the grid pattern is not obvious is layered on the outer periphery of the fine particles, if the thickness is 10% or less of the average particle diameter, the The volume ratio of the amorphous phase in the composite tungsten oxide fine particles is 50% or less.

On the other hand, when the composite tungsten oxide fine particles are dispersed in a matrix of a solid medium such as a resin constituting the composite tungsten oxide fine particle dispersion, if the average particle diameter of the dispersed composite tungsten oxide fine particles is subtracted from the grain diameter, If the difference is less than 20% of the average particle diameter, it can be said that the composite tungsten oxide fine particles belong to a single crystal whose volume ratio of the amorphous phase is 50% or less.

According to the above matters, it is preferable that The difference between the average particle diameter of the composite tungsten oxide microparticles in the particle dispersion minus the crystal grain diameter is less than 20% of the average particle diameter, and the synthesis steps of the composite tungsten oxide microparticles are appropriately adjusted in accordance with the manufacturing equipment, Crushing step and dispersing step.

Moreover, the measurement of the crystal structure or the lattice constant of the composite tungsten oxide fine particles can be used to identify the composite tungsten oxide fine particles obtained by removing the solvent of the dispersion for forming a near-infrared absorber by X-ray diffraction. The crystal structure contained was calculated as the lattice constant by using the Rietveld method to calculate the a-axis length and the c-axis length.

(2) Particle size and grain diameter

The average particle diameter of the composite tungsten oxide fine particles of the present invention is 100 nm or less. From the viewpoint of exhibiting more excellent near-infrared absorption characteristics, the average particle diameter is preferably 10 nm or more and 100 nm or less, more preferably 10 nm or more and 80 nm or less, and even more preferably 10 nm or more and 60 nm or less. When the average particle diameter is in a range of 10 nm to 60 nm, the most excellent near-infrared absorption characteristics are exhibited.

Here, the average particle diameter refers to a diameter value possessed by each of the composite tungsten oxide fine particles that are not aggregated, and is an average particle diameter of the composite tungsten oxide fine particles contained in the composite tungsten oxide fine particle dispersion described later.

On the other hand, this average particle diameter does not include the diameter of the aggregates of the composite tungsten oxide fine particles, and is different from the dispersed particle diameter.

The average particle diameter is calculated from an electron microscope image of the composite tungsten oxide fine particles.

The average particle diameter of the composite tungsten oxide fine particles contained in the composite tungsten oxide fine particle dispersion is the thinness of the composite tungsten oxide fine particle dispersion obtained from the cross-section processing. A transmission electron microscope image of the tabletized sample was used to measure the particle diameters of 100 composite tungsten oxide fine particles using an image processing device, and the average value was calculated and obtained. The cross-section processing for taking out the sliced sample can use a slicer, a cross-section polisher, a focused ion beam (FIB, Focused Ion Beam) device, and the like. In addition, the average particle diameter of the composite tungsten oxide microparticles contained in the composite tungsten oxide microparticle dispersion is an average value of the particle diameters of the composite tungsten oxide microparticles dispersed in a solid medium of the matrix.

From the viewpoint of exhibiting excellent infrared absorption characteristics, the grain diameter of the composite tungsten oxide fine particles is preferably 10 nm or more and 100 nm or less, more preferably 10 nm or more and 80 nm or less, and even more preferably 10 nm or more and 60 nm or less. When the crystal grain diameter is in a range of 10 nm to 60 nm, the most excellent near-infrared absorption characteristics can be exhibited.

Moreover, the lattice constant or grain diameter of the composite tungsten oxide fine particles contained in the composite tungsten oxide fine particle dispersion liquid obtained by the disintegration treatment, pulverization treatment, or dispersion treatment described later is dispersed from the composite tungsten oxide fine particles. The composite tungsten oxide fine particles obtained by removing volatile components from the liquid, or the composite tungsten oxide fine particles contained in the composite tungsten oxide fine particle dispersion obtained from the composite tungsten oxide fine particle dispersion are maintained.

As a result, the effect of the present invention can also be exhibited in the composite tungsten oxide fine particle dispersion liquid or the composite tungsten oxide fine particle dispersion containing the composite tungsten oxide fine particle of the present invention.

(3) Composition of composite tungsten oxide particles

The composite tungsten oxide fine particles of the present invention are preferably of the general formula M _x W _y O _z (wherein 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, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb, W is tungsten, O is oxygen, and 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0).

The composite tungsten oxide fine particles represented by the general formula M _x W _y O _z z will be described.

The element M, x, y, z and its crystal structure in the general formula M _x W _y O _z are closely related to the free electron density of the composite tungsten oxide particles, and have a great influence on the near-infrared absorption characteristics.

Generally speaking, since there is no effective free electron in tungsten trioxide (WO ₃ ), the near-infrared absorption characteristic is low.

Here, the inventors of the present case found that by adding an M element to the tungsten oxide (where the M element is selected from the group consisting of 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, Yb)) to make a composite tungsten oxide, then Tungsten oxide generates free electrons, and exhibits absorption characteristics from free electrons in the near-infrared region, becoming effective as a near-infrared absorbing material with a wavelength of around 1000 nm, and the composite tungsten oxide system maintains a chemically stable state and becomes effective as a weathering superior Near-infrared absorbing material. In addition, the M element is preferably Cs, Rb, K, Tl, Ba, In, and if the M element is CS or Rb, the composite tungsten oxide is easily formed into a hexagonal structure. As a result, visible light penetrates, absorbs near-infrared rays, and is converted into heat. The reasons described below are particularly good. In addition, when two or more elements are selected as the M element, one of them is selected from Cs, Rb, K, Tl, Ba, and In, and the remaining is selected from one or more elements constituting the M element, and may sometimes become a hexagonal crystal.

Here, the discovery by the inventors of the present invention about the value of x indicating the amount of M element added will be described.

When the x / y value is 0.001 or more, a sufficient amount of free electrons are generated and the near-infrared absorption characteristics of the target can be obtained. In addition, the more the M element is added, the more the free electrons are supplied, and the near-infrared absorption characteristics are also improved, but the effect is saturated when the x / y value is about 1. In addition, if the x / y value is 1 or less, it is preferable to avoid generation of an impurity phase in the composite tungsten oxide fine particles.

Next, the discovery by the present inventors of the present invention of the z value indicating the control of the amount of oxygen will be described.

In the composite tungsten oxide fine particles represented by the general formula M _x W _y O _z , the z / y value is preferably 2.0 ≦ x / y ≦ 3.0, more preferably 2.2 ≦ z / y ≦ 3.0, and even more preferably 2.6 ≦ z / y ≦ 3.0, preferably 2.7 ≦ z / y ≦ 3.0. The reason is that if the z / y value is 2.0 or more, the crystalline phase of WO _{2 which} is not the target can be avoided in the composite tungsten oxide, and the chemical stability of the material can be obtained, so it can be applied as effective Of infrared absorbing material. On the other hand, if the z / y value is 3.0 or less, a required amount of free electrons is generated in the tungsten oxide, and it becomes an infrared absorbing material with high efficiency.

(4) Surface coating of composite tungsten oxide particles

In order to improve the weatherability of the composite tungsten oxide fine particles, it is preferable to coat at least a part of the surface of the composite tungsten oxide fine particles with a surface coating film containing one or more elements selected from silicon, zirconium, titanium, and aluminum. . These surface coatings are basically transparent It is clear that the visible light transmittance does not decrease due to the addition. The coating method is not particularly limited, and the surface of the composite tungsten oxide fine particles can be covered by adding an alkoxide containing a metal containing the above element to a solution in which the composite tungsten oxide fine particles are dispersed. In this case, the surface coating film contains oxygen atoms, but more preferably, the surface coating film is made of an oxide.

(5) Summary

The lattice constant, average particle diameter, and grain diameter of the composite tungsten oxide fine particles described above can be controlled by predetermined synthesis conditions. Specifically, the temperature (firing temperature), the generating time (firing time), the generating environment (firing environment), and precursor raw materials can be generated by the thermo-plasma method or the solid-phase reaction method described later. The morphology, annealing treatment after generation, and doping of impurity elements are appropriately set and controlled. On the other hand, the content rate of the volatile components of the composite tungsten oxide fine particles can be controlled by appropriate setting of manufacturing conditions such as the storage method or storage environment of the fine particles, and the temperature, drying time, and drying method when the fine particle dispersion is dried. . The content of volatile components in the composite tungsten oxide fine particles does not depend on the crystal structure of the composite tungsten oxide fine particles, or a synthesis method such as a thermoplasma method or a solid phase reaction described later.

[b] Synthesis method of composite tungsten oxide fine particles

A method for synthesizing the composite tungsten oxide fine particles of the present invention will be described.

As a method for synthesizing the composite tungsten oxide fine particles of the present invention, for example, a thermoplasma method in which a tungsten compound starting material is put into a thermoplasma, or a solid phase in which a tungsten compound starting material is heat-treated in a reducing gas environment is exemplified. Reaction method. The composite tungsten oxide fine particles synthesized by the thermo-plasma method or the solid-phase reaction method are subjected to dispersion treatment or pulverization, Decentralized processing.

The composite tungsten oxide fine particles synthesized by (1) the thermoplasma method, (2) the solid-phase reaction method, and (3) will be described in this order.

(1) Thermoplasma method

Regarding the thermo-plasma method, (i) the raw materials used in the thermo-plasma method, (ii) the thermo-plasma method and its conditions are explained in order.

(i) Raw materials used in the thermal plasma method

When synthesizing the composite tungsten oxide fine particles of the present invention according to the thermoplasma method, a tungsten compound and a mixed powder with an M element compound can be used as raw materials.

The tungsten compound is preferably selected from the group consisting of tungstic acid (H ₂ WO ₄ ), ammonium tungstate, tungsten hexachloride, tungsten hydrate dissolved in alcohol-added tungsten hexachloride, and hydrolyzed to evaporate the solvent. 1 or more.

In addition, as the M element compound, one or more selected from the group consisting of oxides, hydroxides, nitrates, sulfates, chlorides, and carbonates of the M element are preferably used.

M _x W _y O _z (where M is the above M element, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0) As the ratio of the element to the W element, an aqueous solution containing the tungsten compound and the M element compound is wet-mixed. Then, the obtained mixed liquid is dried to obtain a mixed powder of an M element compound and a tungsten compound. The mixed powder can be used as a raw material for the thermo-plasma method.

In addition, the mixed powder is calcined in the first stage to obtain a composite tungsten oxide under an inert gas monomer or a mixed gas environment of an inert gas and a reducing gas. This composite tungsten oxide can also be used as a raw material for the thermo-plasma method. In addition, firing is performed in a mixed gas environment of an inert gas and a reducing gas in the first stage, and the fired product in the first stage is fired in an inert gas environment in the second stage. The obtained composite tungsten oxide can also be used as a raw material for the thermoplasma method.

(ii) Thermoplasma method and its conditions

As the thermo-plasma used in the present invention, for example, any one of a DC arc plasma, a high-frequency plasma, a microwave plasma, and a low-frequency AC plasma may be applied, or those plasmas may overlap, or by applying a DC plasma The plasma generated by the electric method of the magnetic field, the plasma generated by irradiation with a high output laser, and the plasma generated by a high output electron beam or ion beam. Among them, no matter what kind of thermo-plasma is used, it is preferably a thermo-plasma having a high-temperature portion of 10,000 to 15,000 K, especially a plasma that can control the generation time of fine particles.

The raw material supplied to the thermo-plasma having a high-temperature portion is instantaneously evaporated in the high-temperature portion. Then, the evaporated raw material is condensed in the process of reaching the plasma tail flame, and is rapidly condensed outside the plasma flame to form composite tungsten oxide particles.

Taking a case of using a high-frequency plasma reaction device as an example, a synthesis method will be described with reference to FIG. 1.

First, the inside of the reaction system composed of the inside of the water-cooled quartz double tube and the inside of the reaction container 6 was vacuum-evacuated to about 0.1 Pa (about 0.001 Torr) by a vacuum exhaust device. After the inside of the reaction system is vacuum-sucked, the reaction system is filled with argon gas to make a 1-pressure argon gas flow system.

Thereafter, a plasma gas supply nozzle 4 is introduced into the reaction vessel at a flow rate of 30 to 45 L / min to introduce a gas selected from argon, a mixed gas of argon and helium (Ar-He mixed gas), or a mixed gas of argon and nitrogen ( Ar-N ₂ mixed gas) is used as a plasma gas. On the other hand, an Ar-He mixed gas is introduced from the sheath flow gas supply nozzle 3 at a flow rate of 60 to 70 L / min as a sheath flow gas flowing around the vicinity of the plasma region.

Then, an alternating current is applied to the high-frequency coil 2 to generate a thermo-plasma 1 by a high-frequency electromagnetic field (frequency 4 MHz). At this time, the high-frequency power is set to 30 to 40 kW.

Furthermore, through the powder supply nozzle 5, the mixed powder of the M element compound and the tungsten compound or the composite tungsten oxide obtained by the above synthesis method is used as a carrier with 6 to 98 L / min of argon gas supplied from a gas supply device. The gas is introduced into the thermo-plasma according to the ratio of the supply speed of 25 to 50 g / min for a predetermined time. After the reaction, the generated composite tungsten oxide fine particles are accumulated on the filter 8 through the suction pipe 7 and are therefore collected.

The flow rate of the carrier gas and the feed rate of the raw materials greatly affect the generation time of the fine particles. Therefore, the carrier gas flow rate is preferably set to 6 L / min or more and 9 L / min or less, and the raw material supply rate is set to 25 to 50 g / min.

The plasma gas flow rate is preferably 30 L / min or more and 45 L / min or less, and the sheath gas flow rate is preferably 60 L / min or more and 70 L / min or less. The plasma gas system has the function of maintaining the thermo-plasma area in the high temperature part of 10000 ~ 15000K. The sheath flow gas system cools the inner wall surface of the quartz torch in the reaction vessel, and has the function of preventing the quartz torch from melting. At the same time, because the plasma gas and sheath flow gas affect the shape of the plasma area, these gas flows become important parameters for controlling the shape of the plasma area. As the flow rate of plasma gas and sheath flow gas increases, the shape of the plasma area extends toward the gas flow direction, and the temperature gradient of the plasma tail flame becomes gentle. Therefore, the generation time of the generated particles increases and crystals can be formed. Fine particles.

In the case where the grain diameter of the composite tungsten oxide that can be synthesized by the thermoplasma method exceeds 200 nm, or the compound tungsten oxide compound that can be synthesized by the thermoplasma method In the case where the dispersed particle diameter of the composite tungsten oxide in the composite tungsten oxide fine particle dispersion exceeds 200 nm, pulverization and dispersion treatment described later can be performed. In the case of synthesizing composite tungsten oxide by the thermoplasma method, if the plasma conditions or the subsequent pulverization and dispersion processing conditions are appropriately selected, the average particle diameter, grain diameter, and lattice constant of the composite tungsten oxide are determined The pulverization conditions (micronization conditions) of the a-axis length or the c-axis length can exhibit the effects of the present invention.

(2) Solid-phase reaction method

Regarding the solid-phase reaction method, (i) raw materials used in the solid-phase reaction method, (ii) firing and conditions of the solid-phase reaction method are described in order.

(i) Raw materials used in the solid phase reaction method

When the composite tungsten oxide fine particles of the present invention are synthesized by a solid-phase reaction method, a tungsten compound and an M element compound are used as raw materials.

The tungsten compound is preferably one selected from the group consisting of tungstic acid (H ₂ WO ₄ ), ammonium tungstate, tungsten hexachloride, and tungsten hydrate dissolved by adding water to tungsten hexachloride dissolved in alcohol to hydrolyze and evaporate the solvent. the above.

In addition, the general formula M _x W _y O _z (where M is one or more elements selected from the group consisting of Cs, Rb, K, Tl, Ba, and In, 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0) The M element compound used in the production of the raw materials of the composite tungsten oxide fine particles represented by the compound T is preferably selected from the oxides, hydroxides, nitrates, sulfates, chlorides, One or more carbonates.

A compound containing one or more impurity elements selected from the group consisting of Si, Al, and Zr (hereinafter referred to as "impurity element compounds" in the present invention) may be contained as a raw material. This impurity element compound does not react with the composite tungsten compound in the subsequent firing step, inhibits the crystal growth of the composite tungsten oxide, and has the effect of preventing crystal coarsening. The compound containing an impurity element is preferably one or more selected from the group consisting of oxides, hydroxides, nitrates, sulfates, chlorides, and carbonates, and particularly preferably colloidal silica or colloids having a particle size of 500 nm or less. Alumina.

M _x W _y O _z (where M is the above M element, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1.0, 2.0 ≦ z / y ≦ 3.0) As the ratio of the element to the W element, an aqueous solution containing the tungsten compound and the M element compound is wet-mixed. When the impurity element compound is contained as a raw material, wet mixing is performed so that the impurity element compound becomes 0.5% by mass or less. Then, the obtained mixed solution is dried to obtain a mixed powder of an M element compound and a tungsten compound, or a mixed powder of an M element compound and a tungsten compound containing an impurity element compound.

(ii) Firing of solid phase reaction method and its conditions

The mixed powder of the M element compound and the tungsten compound produced by the wet mixing or the mixed powder of the M element compound and the tungsten compound containing the impurity element compound is mixed with an inert gas alone or an inert gas and a reducing gas. In a gas environment, firing is performed in one stage. The firing temperature is preferably close to the temperature at which the composite tungsten oxide fine particles begin to crystallize. Specifically, the firing temperature is preferably 1,000 ° C or lower, more preferably 800 ° C or lower, even more preferably 800 ° C or lower and 500 ° C or higher. Temperature range.

The reducing gas is not particularly limited, and it is preferably H ₂ . When H _{2 is} used as the reducing gas, the concentration may be appropriately selected in accordance with the firing temperature and the amount of the starting material, and is not particularly limited. For example, it is 20% by volume or less, preferably 10% by volume or less, and more preferably 7% by volume or less. If the concentration of the reducing gas is 20% by volume or less, it is possible to avoid the formation of WO ₂ without a solar radiation absorption function due to rapid reduction. At this time, by controlling the firing conditions, the average particle diameter, crystal grain diameter, and a-axis length or c-axis length of the composite tungsten oxide fine particles of the present invention can be set to predetermined values.

In particular, in the synthesis of the composite tungsten oxide fine particles, tungsten trioxide can be used instead of the above-mentioned tungsten compound.

(3) Synthesized composite tungsten oxide fine particles

When using the composite tungsten oxide fine particles obtained by the thermoplasma method or the solid-phase reaction synthesis method to produce a composite tungsten oxide fine particle dispersion solution described later, the dispersion particle size of the fine particles contained in the dispersion solution may exceed 200 nm. In this case, pulverization and dispersion treatment may be performed in a step of producing a composite tungsten oxide fine particle dispersion liquid described later. Then, if the values of the average particle diameter, the crystal grain diameter, and the a-axis length or c-axis length of the composite tungsten oxide fine particles obtained through the pulverization and dispersion treatment are within the scope of the present invention, the composite tungsten of the present invention The oxide fine particles or the composite tungsten oxide fine particle dispersion obtained from the dispersion liquid can achieve superior near-infrared absorption characteristics.

As described above, the average particle diameter of the composite tungsten oxide fine particles of the present invention is 100 nm or less.

Here, when the average particle diameter of the composite tungsten oxide fine particles obtained by the method described in "[b] Synthesis method of composite tungsten oxide fine particles" exceeds 100 nm, the composite of the present invention can be manufactured by the following steps. Tungsten oxide fine particles: a step of pulverizing and dispersing the particles to produce a composite tungsten oxide fine particle dispersion liquid (pulverizing and dispersing treatment steps); Drying was performed to remove volatile components (almost solvent).

Hereinafter, (i) a pulverization and dispersion process step, and (ii) a drying step will be described in this order.

(i) Crushing and dispersing process steps

The step of pulverizing and dispersing the composite tungsten oxide fine particles is to prevent the composite tungsten oxide fine particles, together with a dispersant described later, in a monomer of a suitable non-hardened thermosetting resin or a suitable solvent described later without agglutination. Evenly dispersed steps.

The pulverizing and dispersing treatment step can ensure that the average particle diameter of the composite tungsten oxide fine particles is 100 nm or less, preferably 10 nm or more and 100 nm or less, and ensure that the crystal lattice constant is 7.3850Å or more and 7.4186Å on the a-axis. Hereinafter, the value of [c-axis lattice constant / a-axis lattice constant] of the c-axis is 7.5600 Å or more and 7.6240 Å or less is more preferably in the range of 1.0221 to 1.0289.

Specifically, for example, a method using a bead mill, a ball mill, a sand mill, a pigment shaker, an ultrasonic homogenizer, and the like for pulverizing and dispersing treatment for a predetermined time can be mentioned. Among them, bead mills, ball mills, sand mills, pigment shakers, and other media agitating mills using a bead ball, a ball, an Ottawa sand, and other media are used to pulverize and disperse them. It takes less time to disperse the particle size, so it is preferred.

When the composite tungsten oxide fine particles are dispersed in the dispersion liquid by pulverizing and dispersing treatment using a medium stirring mill, the composite tungsten oxide fine particles are caused to collide with each other, or the medium particles collide with the fine particles. It is also progressing to make the composite tungsten oxide fine particles more micronized and dispersed (that is, pulverized and dispersed).

With the mechanical dispersion treatment step using these devices, the composite tungsten oxide fine particles are dispersed in the solvent, and the composite tungsten oxide fine particles collide with each other. Micronization is performed, and the crystal structure of hexagonal crystals contained in the composite tungsten oxide particles is strained or deformed. The overlapping state of the electron orbitals of the atoms constituting the grain structure is changed, and the amount of free electrons is increased.

In addition, the micronization of the composite tungsten oxide microparticles and the variation in the a-axis length or c-axis length of the lattice constant in the crystal structure of the hexagonal crystal depend on the device constant of the pulverizer. Therefore, it is important to perform experimental pulverization in advance to obtain a pulverizing device and pulverizing conditions that can provide the predetermined average particle diameter, crystal grain diameter, and a-axis length or c-axis length of the composite tungsten oxide fine particles as described above.

The state of the composite tungsten oxide fine particle dispersion can be confirmed by measuring the dispersion state of the composite tungsten oxide fine particles when the composite tungsten oxide fine particles are dispersed in a solvent. For example, a sample of a sample collected from a liquid in which the composite tungsten oxide fine particles of the present invention exist in a solvent in an aggregated state of the fine particles and the fine particles can be confirmed by measuring with various commercially available particle size distribution meters. As the particle size distribution meter, for example, a known measuring device such as ELS-8000 manufactured by Otsuka Electronics Co., Ltd. based on a dynamic light scattering method can be used.

The dispersed particle diameter of the composite tungsten oxide fine particles of the present invention is preferably 200 nm or less, and more preferably the dispersed particle size is 10 nm or more and 200 nm or less.

The near-infrared absorbing component containing the composite tungsten oxide fine particles of the present invention substantially absorbs light in the near-infrared region, especially near a wavelength of 900 to 2200 nm, so its transmission hue under visible light becomes blue to green Situation. On the other hand, if the dispersed particle diameter of the composite tungsten oxide fine particles contained in the near-infrared absorbing layer is 1 to 200 nm, light scattering in the visible light region with a wavelength of 380 to 780 nm will not be caused by geometrical scattering or Mie scattering. The infrared absorbing layer is caused by a reduction in coloration caused by light scattering, and can be caused by an increase in visible light transmittance. Furthermore, Yu Lei Since the scattered light area is reduced in proportion to the 6th power of the particle size, the scattering area is reduced and the transparency is improved as the dispersed particle size is reduced. Therefore, when the dispersed particle diameter is 200 nm or less, scattered light becomes very small, and the transparency is further increased and improved.

From the above, if the dispersed particle diameter of the fine particles is less than 200 nm, transparency can be ensured, and thus the near-infrared curing ink composition is easily colored. When transparency is important, the dispersed particle diameter is set to 150 nm or less, and more preferably 100 nm or less. On the other hand, when the dispersed particle diameter is 10 nm or more, industrial production becomes easy.

Here, the dispersion particle diameter of the composite tungsten oxide fine particle dispersion liquid will be briefly described. The dispersed particle diameter of the composite tungsten oxide fine particles means the particle diameter of the monomer particles of the composite tungsten oxide fine particles dispersed in the solvent, or the particles (aggregated particles) agglomerated by the composite tungsten oxide fine particles, and is commercially available. Various particle size distribution meters were used for measurement. For example, a sample of the composite tungsten oxide fine particle dispersion liquid can be collected, and the sample can be measured using ELS-8000 manufactured by Otsuka Electronics Co., Ltd. based on the principle of dynamic light scattering.

In addition, the composite tungsten oxide fine particle dispersion having a content of the composite tungsten oxide fine particles obtained by the above-mentioned synthesis method of 0.01% by mass or more and 80% by mass or less has excellent stability of the system liquid. In the case of selecting an appropriate liquid medium, or dispersant, coupling agent, and surfactant, even if placed in a constant temperature bath at a temperature of 40 ° C, gelation of the dispersion liquid or sedimentation of particles does not occur for more than 6 months. , Can maintain the dispersed particle size in the range of 10 ~ 200nm.

Moreover, the dispersion particle diameter of the composite tungsten oxide fine particle dispersion liquid may be different from the average particle diameter of the composite tungsten oxide fine particle dispersed in the composite tungsten oxide fine particle dispersion. This is because even if the composite tungsten oxide fine particle aggregates in the composite tungsten oxide fine particle dispersion, the composite tungsten oxide fine particle dispersion is processed into a complex compound. Tungsten oxide fine particle dispersion is caused by agglomeration and decomposition of composite tungsten oxide fine particles.

(ii) drying step

The drying step is a step of drying the composite tungsten oxide fine particle dispersion liquid obtained through the above-mentioned pulverizing and dispersing steps to remove volatile components in the dispersion liquid to obtain the composite tungsten oxide fine particles of the present invention.

As the equipment for the drying treatment, from the viewpoints of heating and / or decompression, and easy mixing or recovery of the fine particles, an air dryer, a universal mixer, a belt mixer, a vacuum flow dryer, A vibration flow dryer, a freeze dryer, a cone-type belt dryer, a rotary kiln, a spray dryer, a pulverizer dryer, and the like are not limited thereto.

[c] Uncured thermosetting resin

The non-hardened thermosetting resin of the present invention is an unhardened liquid at the time of the near-infrared-curable ink composition, but when it is irradiated with near-infrared, it is given thermal energy from the composite tungsten oxide fine particles. A thermosetting resin that is cured.

Specific examples of the unhardened thermosetting resin include epoxy resin, urethane resin, acrylic resin, urea resin, melamine resin, phenol resin, ester resin, polyimide resin, and polysilicon. Uncured resins such as oxygen resins and unsaturated polyester resins.

In addition, the uncured thermosetting resin may contain a monomer or oligomer that forms a thermosetting resin by a curing reaction, and a known curing agent that is appropriately added. Further, a known curing accelerator may be added to the curing agent.

[d] Other ingredients

The near-infrared curable ink composition of the present invention further contains other components such as a pigment, a solvent, and a dispersant, as necessary.

Therefore, (1) a pigment and a dye, (2) a dispersant, and (3) a solvent will be described in order below.

(1) Pigments and dyes

As the pigment that can be used for coloring the near-infrared curable ink composition of the present invention, known pigments can be used without particular limitation. Specifically, organic pigments such as insoluble pigments and lake pigments, and inorganic pigments such as carbon black are preferably used.

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

As described above, the insoluble pigment is not particularly limited, and examples thereof include azo, methine azo, methine, diphenylmethane, triphenylmethane, quinacridone, anthraquinone, perylene, indigo, quinoline yellow, isopropyl Indolinone, isoindolin , Thi ,two , Thiazole, phthalocyanine, pyrrolopyrrole dione and the like are preferred insoluble pigments.

Here, the names of the commercially available pigments which can be preferably used are listed below.

Examples of magenta or red pigments include CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 15, CI Pigment Red 16, and CI Pigment Red 48: 1, CI Pigment Red 53: 1, CI Pigment Red 57: 1, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 139, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 202, CI Pigment Red 222, CI Pigment Violet 19 and the like.

Examples of orange or yellow pigments include C.I. Pigment Orange 31, CI Pigment Orange 43, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 15: 3, CI Pigment Yellow 17, CI Pigment Yellow 74, CI Pigment Yellow 93, CI Pigment Yellow 128, CI Pigment Yellow 94, CI Pigment Yellow 138, etc.

Examples of green or cyan blue pigments 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, C.I. Pigment Green 7, and the like.

Examples of black pigments include C.I. Pigment Black 1, C.I. Pigment Black 6, C.I. Pigment Black 7, and the like.

As described above, the inorganic pigment is not particularly limited, and includes carbon black, titanium dioxide, zinc sulfide, zinc oxide, zinc phosphate, mixed oxide metal phosphate, iron oxide, iron manganese oxide, chromium oxide, ultramarine blue, nickel, or chromium antimony titanium oxide. Compounds, cobalt oxide, aluminum, aluminum oxide, silicon oxide, silicate, zirconia, mixed oxides of cobalt and aluminum, molybdenum sulfide, rutile mixed phase pigments, rare earth sulfides, bismuth vanadate, aluminum hydroxide Or an organic pigment such as barium sulfate is a preferable inorganic pigment.

The dispersed particle diameter of the pigment in the dispersed state contained in the near-infrared curable ink composition of the present invention is preferably from 10 nm to 200 nm. The reason is that if the dispersed particle diameter of the pigment dispersion is 10 nm or more and 200 nm or less, the storage stability in the near-infrared curing ink composition is good.

The dye used in the present invention is not particularly limited, and either an oil-soluble dye or a water-soluble dye can be used, and preferably a yellow dye, a magenta dye, a cyan blue dye, or the like can be used.

Examples of the yellow dye include aryl or heteroaryl azo dyes having phenols, naphthols, anilines, pyrazolinones, pyridones, and open-chain active methylene compounds as coupling components. ; For example, an open-chain active methylene compound is used as an methine azo dye in the coupling component; for example, a benzylidene dye or a monomethine cyanine dye; for example, a naphthoquinone dye, anthracene Quinone dyes such as quinone dyes. Examples of dyes other than this include quinoline yellow dye, nitro-nitroso dye, acridine dye, and acridone dye.

These dyes may be partially dissociated from the chromophore and initially appear yellow. The relative cation at this time may be an alkali metal or an inorganic cation such as ammonium, or an organic cation such as pyridinium or a quaternary ammonium salt, and may also be a polymer cation having these in some structures.

As the magenta dye, for example, aryl or heteroaryl azo dyes having phenols, naphthols, and anilines as coupling components; for example, pyrazolinones and pyrazolotriazoles as coupling components Methine azo dyes; for example, arylene dyes, styryl dyes, merocyanine dyes, oxacyanine dyes; for example, diphenylmethane dyes, triphenylmethane dyes, Dye-like carbocation dyes; such as naphthoquinone, anthraquinone, and anthrapyridone; quinone dyes; Polycyclic dyes such as dyes and the like.

These dyes may be partially dissociated from the chromophore and initially exhibit a magenta color. The relative cation at this time may be an alkali metal or an inorganic cation such as ammonium. It may also be an organic cation such as pyridinium or a quaternary ammonium salt. Furthermore, it may be a polymer cation having these in some structures.

Examples of the cyan dye include indigoaniline dyes and indoxyphenol dyes; methine azo dyes; cyanine dyes, oxacyanine dyes, and merocyanine dyes; polyphenylmethane dyes; and diphenylmethane. Dyes, triphenylmethane dyes, Dye-like carbocation dyes; phthalocyanine dyes; anthraquinone dyes; for example, aryl or heteroaryl azo dyes with phenols, naphthols, and anilines as coupling components; indigo ‧ thioindigo dyes.

These dyes may be partially dissociated from the chromophore and initially appear cyan. The relative cation at this time may be an alkali metal or an inorganic ammonium cation, or an organic cation such as pyridinium or a quaternary ammonium salt. Furthermore, it may be a polymer cation having these in some structures. A black dye such as a polyazo dye may also be used.

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.

As the water-soluble dye, specific dye names which can be preferably used are listed below.

For example, CI 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, 21, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, CI Direct Purple 7, 9, 47, 48, 51 , 66, 90, 93, 94, 95, 98, 100, 101, CI 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, CI 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, CI directly 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, CI Acid Red 35, 42 , 52, 57, 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, CI Acid Violet 5, 34, 43, 47, 48, 90, 103, 126, CI 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, CI Acid Black 7, 24, 29, 48, 52: 1, 172, CI reactive red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55, CI reactive red 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34, CI Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42, CI Reactive Blue 2, 3, 5, 8, 10, 13, 14, 15, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38, CI Reactive Black 4, 5, 8, 14, 21, 23, 26, 31, 32, 34, CI Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46, CI base Sex Violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48, CI Basic Yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40, CI Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71, CI Basic Black 8, etc.

The particle diameter of the pigment or the composite tungsten oxide fine particles of the coloring material contained in the near-infrared curing ink described above is preferably determined in consideration of the characteristics of the coating device of the near-infrared curing ink composition.

Furthermore, the near-infrared-curable ink composition system of the present invention also includes the concept of a near-infrared-curable ink composition that does not contain the above-mentioned pigments and dyes.

(2) Dispersant

The composite tungsten oxide fine particles of the present invention may be dispersed together with a suitable dispersant in a suitable monomer of a thermosetting resin in an unhardened state, or a suitable solvent described later. In the media. By adding an appropriate dispersant, the composite tungsten oxide fine particles can be easily dispersed in the near-infrared hardening ink, and it is expected that the hardening deviation of the coating film of the near-infrared hardening ink can be suppressed.

In addition, as the dispersant, a suitable commercially available dispersant may be used, and it is preferably a polyester-based, polyacrylic-based, polyurethane-based, polyamine-based, polycaprolactone-based, or polystyrene-based. Its main chain serves as a molecular structure of a dispersant, and has an amine group, an epoxy group, a carboxyl group, a hydroxyl group, a sulfonic acid group and the like in a functional group. The dispersant having such a molecular structure is not easily deteriorated when the coating film of the near-infrared curing ink of the present invention is intermittently irradiated with near-infrared for several tens of seconds. As a result, a bad situation caused by the deteriorated coloring and the like does not occur.

Examples of such dispersants include: SOLSPERSE (registered trademark) (the same applies hereinafter) 3000, 5000, 9000, 11200, 12000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, manufactured by Lubrizol, Japan. , 20000, 21000, 24000SC, 24000GR, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 32600, 3600, 33000, 33500, 34750, 35100, 35200, 36600, 37500, 38500, 39000, 41000, 41090, 53095, 55000 , 56000, 71000, 76500, J180, J200, M387, etc .; SOLPLUS (registered trademark) (the same below) D510, D520, D530, D310, K310, K500, L300, L400, R700, etc .; Disperbyk by BYK-Chemie JAPAN (Registered trademark) (the same below)-101, 102, 103, 106, 107, 108, 109, 110, 111, 112, 116, 130, 140, 142, 145, 154, 161, 162, 163, 164, 165 , 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 191, 192, 2000, 2001, 2009, 2020, 2025, 2050, 2070, 2095, 2096, 2150, 2151, 2152, 2155, 2163, 2164; Anti-Terra (registered trademark) (the same applies hereinafter)-U, 203, 204, etc .; BYK (registered trademark) (the same applies hereinafter)-P104, P104S, P105, P9050 , P9051, P9060, P9065, P9080, 051, 052, 053, 054, 055, 057, 063, 065, 066N, 067A, 077, 088, 141, 220S, 300, 302, 306, 307, 310, 315, 320 , 322, 323, 325, 330, 331, 333, 337, 340, 345, 346, 347, 348, 350, 354, 355, 358N, 361N, 370, 375, 377, 378, 380N, 381, 392, 410 , 425, 430, 1752, 4510, 6919, 9076, 9077, W909, W935, W940, W961, W966, W969, W972, W980, W985, W995, W996, W9010, Dynwet800, Siclean3700, UV3500, UV3510, UV3570, etc .; EFKA (registered trademark) manufactured by EFKA Additives (the same applies hereinafter) 2020, 2025, 3030, 3031, 3236, 4008, 4009, 4010, 4015, 4046, 4047, 4060, 4080, 7462, 4020, 4050, 4055, 4300, 4310, 4320, 4400, 4401, 4402, 4403, 4300, 4320, 4330, 4340, 5066, 5220, 6220, 6225, 6230, 6700, 6780, 6782, 8503; JON by BASF Japan CRYL (registered trademark) (the same applies hereinafter) 67, 678, 586, 611, 680, 682, 690, 819, -JDX5050, etc .; TERPLUS (registered trademark) (the same applies hereinafter) MD 1000, D 1180, D 1130, etc .; AJISPER (registered trademark) made by Ajinomoto Fine Techno Co., Ltd. (the same applies to the following) PB-711, PB-821, PB-822, etc .; DISPERLON (registered trademark) (the same applies to the following) made by Nanmoto Chemicals Corporation 1831, 1850, 1860, 1934, DA-400N, DA-703-50, DA-325, DA-375, DA-550, DA-705, DA-725, DA-1401, DA-7301, DN-900, NS-5210, NVI-8514L, etc .; ARUFON (registered trademark) (the same applies hereinafter) UC-3000 , UF-5022, UG-4010, UG-4035, UG-4070, etc.

(3) Solvent

In the near-infrared curable ink composition of the present invention, it is also preferable to use a solvent together with the monomer of the thermosetting resin in an uncured state.

In this case, as a solvent for the near-infrared curing ink composition, it is preferable to use a monomer or oligomer provided with the thermosetting resin contained in the resin which is in an uncured state during a curing reaction of a thermosetting resin described later. Reactive organic solvent with functional groups such as epoxy groups.

By adding this solvent, the viscosity of the near-infrared curable ink composition can be appropriately adjusted. Furthermore, as a result, it is possible to easily secure the coatability or the smoothness of the coating film.

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

[e] Near-infrared curing ink composition

As described above, the composite tungsten oxide fine particles of the present invention are added to an unhardened thermosetting resin, or the composite tungsten oxide fine particles of the present invention are dispersed in an appropriate solvent, and then the unhardened thermosetting resin is added. This can obtain the near infrared hard Chemical ink composition. The near-infrared hardening type ink composition of the present invention is provided on a predetermined substrate and cured by irradiating near-infrared rays, and has excellent adhesion to the substrate.

In addition, the near-infrared hardening ink composition of the present invention is most suitable for coating a predetermined amount, and is irradiated with near-infrared to harden and stack it, in addition to the conventional use as an ink. Near-infrared curable ink composition of light forming method for three-dimensional objects.

As described above, the solvent is removed from the near-infrared hardening type ink composition containing the composite tungsten oxide fine particles and containing the solvent, the dispersant, and the unhardened thermosetting resin; or, without using the solvent, a composite tungsten oxide containing The near-infrared-curable ink composition containing fine particles, a dispersant, and an uncured thermosetting resin is also a preferable structure.

The near-infrared hardening ink composition containing composite tungsten oxide fine particles without a solvent, containing a dispersant, and an unhardened thermosetting resin, can be omitted in the subsequent steps, and related to the volatilization of the solvent. Good efficiency.

On the other hand, the method for removing the solvent is not particularly limited, and a heating distillation method to which a reduced-pressure operation is added can be used.

The amount of the composite tungsten oxide fine particles contained in the near-infrared hardening ink of the present invention may be an amount that can be hardened by appropriately adding a thermosetting resin that is not hardened during the hardening reaction. Therefore, if the coating thickness of the near-infrared curing ink is also considered, the amount of the composite tungsten oxide particles per unit coating area of the near-infrared curing ink may be determined.

The method for dispersing the composite tungsten oxide fine particles in the solvent is not particularly limited, but a wet-type media mill is preferably used. However, at this time, experimental dispersion was also performed in advance, and it was found that the average particle diameter of the composite tungsten oxide fine particles can be 100 nm or more. Below, the lattice constant is more than 7.3850Å and less than 7.4186Å, the c-axis is more than 7.5600Å and less than 7.6240Å. More preferably, the value of [c-axis lattice constant / a-axis lattice constant] is 1.0221. Dispersion device and dispersion conditions above 1.0289.

[2] Near-infrared hardened material and photoforming method

Since the near-infrared curing ink of the present invention has visible light penetrability, a predetermined amount of a coating film is obtained by coating the near-infrared curing ink composition, and the near-infrared radiation is applied to harden the coating film, thereby obtaining a predetermined base. The near-infrared hardened film of the present invention exhibits excellent adhesion. A colored film can be easily obtained by adding at least one or more kinds of various pigments or dyes to the near-infrared curable ink. Since the composite tungsten oxide fine particles in the coloring film hardly affect the color tone, the coloring film can be used in a color filter and the like of a liquid crystal display.

The above-mentioned reason for obtaining excellent adhesion is that the composite tungsten oxide fine particles absorb near-infrared rays to radiate heat, and the heat energy of the heat is promoted by the monomers or oligomers contained in the non-hardened thermosetting resin. Reactions such as polymerization, condensation, or addition reactions cause hardening reactions of thermosetting resins. In addition, due to the heat generation of the composite tungsten oxide fine particles caused by the near-infrared radiation, the solvent is also volatilized.

On the other hand, even if the near-infrared hardened film of the present invention is further irradiated with near-infrared, the hardened film is no longer melted. Since the near-infrared hardening film of the present invention contains a thermosetting resin obtained by curing an unhardened thermosetting resin, even if the composite tungsten oxide fine particles generate heat by irradiation with near-infrared rays, they will no longer melt.

This characteristic is applied to harden and stack the near-infrared curable ink composition of the present invention, and repeatedly repeat the near-infrared curable ink. It is especially effective to apply the laminated layer with near-infrared irradiation to form a three-dimensional object in a light shaping method, which is supplemented with the above-mentioned superior adhesion to the substrate.

Of course, it is also preferable to apply a predetermined amount of the near-infrared curable ink composition of the present invention to a substrate and irradiate the near-infrared to harden it, thereby obtaining the near-infrared cured film of the present invention.

The material of the substrate used in the present invention is not particularly limited. For various purposes, it is preferable to use, for example, paper, PET, acrylic, urethane, polycarbonate, polyethylene, ethylene vinyl acetate copolymer, chlorine Ethylene, fluororesin, polyimide, polyacetal, polypropylene, nylon, etc. In addition to paper and resin, glass can be preferably used.

As a method for curing the near-infrared-curable ink composition of the present invention, infrared radiation is preferable, and near-infrared radiation is more preferable. The near-infrared system has a large energy density, and can efficiently impart energy required for the resin in the ink composition to harden.

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

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

Moreover, in the present invention, the term "microwave" means having a range of 1 mm to 1 m. Around the electromagnetic wave.

The irradiated microwave preferably has a power of 200-1000W. If the power is 200W or more, the evaporation of the organic solvent remaining in the ink is promoted. If the power is 1000W or less, the irradiation conditions are relatively gentle, and there is no risk that the substrate or the thermosetting resin will be deteriorated.

The preferred infrared irradiation time for the near-infrared curable ink composition of the present invention varies depending on the energy or wavelength of irradiation, the composition of the near-infrared curable ink, and the coating amount of the near-infrared curable ink, but it is generally preferred Irradiation for 0.1 seconds or more. With an irradiation time of 0.1 seconds or more, infrared irradiation can be performed within a range controlled to the above-mentioned preferable power. It is also possible to sufficiently dry the solvent in the ink composition by extending the irradiation time. However, when printing or coating at high speed is considered, the irradiation time is preferably within 30 seconds, and more preferably within 10 seconds.

As an infrared radiation source, it can be obtained directly from a heat source, or it can also obtain effective infrared radiation from a heat medium. For example, infrared rays can be obtained by discharge lamps such as mercury, xenon, cesium, sodium, or carbon dioxide gas lasers, and by heating resistors such as platinum, tungsten, nichrome, and Kantal. Moreover, as a preferable radiation source, for example, a halogen lamp can be mentioned. Halogen lamps have the advantages of good thermal efficiency and fast warm-up.

The infrared irradiation of the near-infrared-curable ink composition of the present invention may be performed from the side of the near-infrared-curable ink coating surface or from the back side. It is also preferable to perform irradiation from both sides simultaneously, and it is also preferable to perform it in combination with temperature drying or air drying. Moreover, it is more preferable to use a light-concentrating plate as needed. By combining these methods, they can be hardened by short-term infrared irradiation.

[Example]

The following examples illustrate the invention more specifically. However, the present invention is not limited to these examples.

(1) Measurement method of crystal structure, calculation method of lattice constant and crystal grain diameter

As the sample to be measured for the composite tungsten oxide fine particles, a composite tungsten oxide fine particle obtained by removing a solvent from a dispersion liquid for forming a near-infrared absorber was used. The X-ray diffraction pattern of the composite tungsten oxide particles is a powder X-ray diffraction method using a powder X-ray diffraction device (X'Pert-PRO / MPD, manufactured by Spectris Corporation, PANalytical). (θ-2θ method) measurement. The crystal structure contained in the fine particles was specified from the obtained X-ray diffraction pattern, and the lattice constant and crystal grain diameter were calculated using the Rietwald method.

(2) Dispersion particle size

The dispersed particle diameter of the fine particles in the composite tungsten oxide fine particle dispersion is determined by using dynamic light scattering method (photon correlation method) by observing the disturbance of scattered light by laser using ELS-8000 manufactured by Otsuka Electronics Co., Ltd. The autocorrelation function calculates the average particle size (diameter of hydrodynamics) by the cumulative method.

(3) Evaluation of hardened film containing composite tungsten oxide particles

A 3 mm thick blue plate glass plate was coated with a near-infrared hardening ink composition, and was irradiated with near-infrared to produce a hardened film containing composite tungsten oxide particles. The optical characteristics of the cured film were measured using a spectrophotometer U-4100 (manufactured by Hitachi, Ltd.). The visible light transmittance is measured in accordance with JIS R 3106: 1998.

(4) Average particle size in hardened film containing composite tungsten oxide particles

Composite tungsten oxide particles dispersed in a near-infrared hardening ink composition The average particle diameter of s was measured by observing a transmission electron microscope image of the cross section of the cured film. The image of the transmission electron microscope was observed using a transmission electron microscope (HF-2200 manufactured by Hitachi Advanced Technology). This transmission electron microscope image was processed by an image processing device, and the particle diameter of 100 composite tungsten oxide fine particles was measured, and the average value was used as the average particle diameter.

[Example 1]

Dissolve 7.43 kg of cesium carbonate (Cs ₂ CO ₃ ) in 6.70 kg of water to obtain a solution. This solution was added to 34.57 kg of tungstic acid (H ₂ WO ₄ ), and after sufficiently stirring and mixing, it was dried while stirring (the molar ratio of W and Cs is equivalent to 1: 0.33). The dried product was heated while supplying 5 vol% H ₂ gas using N ₂ gas as a carrier, and calcined at 800 ° C. for 5.5 hours. Thereafter, the supply gas was switched to only N ₂ gas, and the temperature was reduced to Composite tungsten oxide particles (hereinafter referred to as particles a) were obtained at room temperature.

20 parts by mass of mixed particles a, 65 parts by mass of methyl isobutyl ketone, and 15 parts by mass of an acrylic dispersant were used as a mixture. Fill this mixture until 0.3mm is added ZrO ₂ bead pigment shaker (manufactured by Asada Iron Industry Co., Ltd.) was pulverized and dispersed for 7 hours to obtain a micronized particle a (hereinafter referred to as a microparticle a) microparticle dispersion (hereinafter referred to as a microparticle dispersion) a). At this time, 0.3 mm was used with respect to 100 parts by mass of the mixture. 300 parts by mass of ZrO ₂ beads were pulverized and dispersed.

Here, the dispersed particle size of the fine particles a in the fine particle dispersion liquid a was measured using a particle size measuring device (ELS-8000, manufactured by Otsuka Electronics Co., Ltd.) according to a dynamic light scattering method, and the result was 70 nm. Further, the lattice constants of the fine particles a after the solvent was removed from the fine particle dispersion liquid a were measured. As a result, the a-axis system was 7.4008Å and the c-axis system was 7.6122Å. The crystal grain diameter was 24 nm. Furthermore, a crystal structure of hexagonal crystals was confirmed.

25 parts by mass of the fine particle dispersion liquid a was mixed with 75 parts by mass of MEG Screen Ink (medium), a thermosetting ink containing an uncured thermosetting resin (made by Imperial Ink Manufacturing Co., Ltd.), which is a commercially available liquid type. The near-infrared curable ink of Example 1 (hereinafter referred to as ink A).

Ink A was coated on a blue plate glass with a thickness of 3 mm using a bar coater (No. 10), and a LINE HEATER HYP-14N (output 980 W) manufactured by HYBEC Co., Ltd., which is a near-infrared irradiation source, was set to the pitch coating. The cloth surface had a height of 5 cm and was irradiated with near-infrared rays for 10 seconds to obtain a cured film of Example 1 (hereinafter referred to as cured film A).

The average particle diameter of the composite tungsten oxide fine particles dispersed in the cured film A was calculated by an image processing apparatus using a transmission electron microscope image, and it was 25 nm.

The adhesiveness of the cured film A was evaluated by the following method.

Use a cutting guide with a gap of 1mm to cut 100 square-shaped cuts, and attach 18mm wide tape (made by NICHIBAN) CELLOTAPE (registered trademark) CT-18 to the cut surface on the square After the roller of 2.0 kg was moved back and forth 20 times to make it fully adhere, it was quickly peeled off at a peeling angle of 180 degrees to calculate the number of squares to be peeled.

The number of stripped squares is 0.

Even when the cured film A was irradiated with near-infrared rays under the same conditions as when the near-infrared curing ink was cured for 20 seconds, the cured film did not re-melt.

The above results are shown in Tables 1 and 2.

[Example 2]

The same operation as in Example 1 was performed except that the predetermined amounts of tungstic acid and cesium carbonate were measured in such a manner that the molar ratio of W and Cs became 1: 0.31. Cs tungsten oxide fine particles (hereinafter referred to as fine particles b).

A dispersion liquid of fine particles b (hereinafter referred to as fine particle dispersion liquid b) was obtained in the same manner as in Example 1 except that fine particles b were used instead of fine particles a.

Next, except that the fine particle dispersion liquid a was used instead of the fine particle dispersion liquid b, the same operation as in Example 1 was performed to prepare a near-infrared curing ink of Example 2 (hereinafter referred to as ink B).

A cured film of Example 2 (hereinafter referred to as cured film B) was obtained in the same manner as in Example 1 except that ink B was used instead of ink A.

The microparticle dispersion liquid b and the cured film B were evaluated in the same manner as in Example 1. Further, a hexagonal crystal structure was confirmed in the composite tungsten oxide fine particle sample.

The above results are shown in Tables 1 and 2.

[Example 3]

The Cs tungsten oxide fine particles (hereinafter referred to as fine particles) of Example 3 were obtained in the same manner as in Example 1 except that the predetermined amounts of tungstic acid and cesium carbonate were measured so that the molar ratio of W and Cs became 1: 0.35. c).

A dispersion liquid of fine particles c (hereinafter referred to as fine particle dispersion liquid c) was obtained in the same manner as in Example 1 except that fine particles c were used instead of fine particles a.

Next, except that the microparticle dispersion liquid c was used instead of the microparticle dispersion liquid a, the same operation as in Example 1 was performed to prepare a near-infrared curing ink of Example 3 (hereinafter referred to as ink C).

A cured film of Example 3 (hereinafter referred to as cured film C) was obtained in the same manner as in Example 1 except that Ink C was used instead of Ink A.

The microparticle dispersion liquid c and the cured film C were evaluated in the same manner as in Example 1. Also, Yu Fu A hexagonal crystal structure was confirmed in the tungsten oxide fine particle sample.

The above results are shown in Tables 1 and 2.

[Example 4]

The Cs tungsten oxide fine particles (hereinafter referred to as fine particles) of Example 4 were obtained in the same manner as in Example 1 except that the predetermined amounts of tungstic acid and cesium carbonate were measured so that the molar ratio of W and Cs became 1: 0.37. d).

A dispersion liquid of fine particles d (hereinafter referred to as fine particle dispersion d) was obtained in the same manner as in Example 1 except that fine particles d were used instead of fine particles a.

Next, except that the microparticle dispersion liquid d was used instead of the microparticle dispersion liquid a, the same operation as in Example 1 was performed to prepare a near-infrared curing ink of Example 4 (hereinafter referred to as ink D).

A cured film of Example 4 (hereinafter referred to as cured film D) was obtained in the same manner as in Example 1 except that Ink D was used instead of Ink A.

The fine particle dispersion liquid d and the cured film D were evaluated in the same manner as in Example 1. Further, a hexagonal crystal structure was confirmed in the composite tungsten oxide fine particle sample.

The above results are shown in Tables 1 and 2.

[Example 5]

A Cs tungsten oxide particle (hereinafter referred to as a fine particle) of Example 5 was obtained in the same manner as in Example 1 except that the predetermined amounts of tungstic acid and cesium carbonate were measured so that the molar ratio of W and Cs became 1: 0.21. e).

A dispersion liquid of fine particles e (hereinafter referred to as a fine particle dispersion liquid e) was obtained in the same manner as in Example 1 except that fine particles e were used instead of the fine particles a.

Next, except that the microparticle dispersion liquid e was used instead of the microparticle dispersion liquid a, the same operation as in Example 1 was performed to prepare a near-infrared curing ink of Example 5 (hereinafter referred to as ink E).

A cured film of Example 5 (hereinafter referred to as cured film E) was obtained in the same manner as in Example 1 except that ink E was used instead of ink A.

The fine particle dispersion liquid e and the cured film E were evaluated in the same manner as in Example 1. Further, a hexagonal crystal structure was confirmed in the composite tungsten oxide fine particle sample.

The above results are shown in Tables 1 and 2.

[Example 6]

Except for supplying 5% H ₂ gas with N ₂ gas as a carrier and firing at a temperature of 550 ° C. for 9.0 hours, the same operation as in Example 1 was performed to obtain Cs tungsten oxide particles of Example 6 (described below) For particles f).

A dispersion liquid of fine particles f (hereinafter referred to as fine particle dispersion liquid f) was obtained in the same manner as in Example 1 except that fine particles f were used instead of fine particles a.

Next, except that the microparticle dispersion liquid a was used instead of the microparticle dispersion liquid a, the same operation as in Example 1 was performed to prepare a near-infrared curing ink of Example 6 (hereinafter referred to as ink F).

A cured film of Example 6 (hereinafter referred to as cured film F) was obtained in the same manner as in Example 1 except that Ink A was used instead of Ink F.

The microparticle dispersion liquid f and the cured film F were evaluated in the same manner as in Example 1. Further, a hexagonal crystal structure was confirmed in the composite tungsten oxide fine particle sample.

The above results are shown in Tables 1 and 2.

[Example 7]

Except that 30 parts by mass of the fine particle dispersion liquid a was mixed with 70 parts by mass of one of the commercially available liquid-type thermosetting inks, the same operation as in Example 1 was performed to prepare a near-infrared curing ink of Example 7 (described below) For ink G).

A cured film of Example 7 (hereinafter referred to as cured film G) was obtained in the same manner as in Example 1 except that ink G was used instead of ink A.

The cured film G was evaluated in the same manner as in Example 1.

The above results are shown in Tables 1 and 2.

[Example 8]

Except that 35 parts by mass of the fine particle dispersion liquid a was mixed with 65 parts by mass of one of the commercially available liquid-type thermosetting inks, the same operation as in Example 1 was performed to prepare a near-infrared curing ink of Example 8 (described below) For ink H).

A cured film of Example 8 (hereinafter referred to as cured film H) was obtained in the same manner as in Example 1 except that ink H was used instead of ink A.

The cured film H was evaluated in the same manner as in Example 1.

The above results are shown in Tables 1 and 2.

[Example 9]

Except that 25 parts by mass of the fine particle dispersion liquid a, 37.5 parts by mass of an unhardened bisphenol A type epoxy resin, and 37.5 parts by mass of a hardening accelerator-added hardener were mixed, the same operation was performed as in Example 1 to prepare an example. Near infrared curing ink of 9 (hereinafter referred to as ink I). In addition, the hardener is a mixture of a phenol resin and an imidazole (hardening accelerator).

A cured film of Example 9 (hereinafter referred to as cured film I) was obtained in the same manner as in Example 1 except that Ink I was used instead of Ink A.

The cured film I was evaluated in the same manner as in Example 1.

The above results are shown in Tables 1 and 2.

[Example 10]

20 parts by mass of particles a, 65 parts by mass of methyl isobutyl ketone, and 15 parts by mass of an acrylic dispersant were mixed to prepare a mixture. Fill this mixture until 0.3mm is added A pigment shaker (manufactured by Asada Iron Works) of ZrO ₂ beads was pulverized and dispersed for 20 minutes to obtain a fine particle dispersion liquid (hereinafter referred to as a fine particle dispersion liquid p) of fine particles a. At this time, 0.3 mm was used with respect to 100 parts by mass of the mixture. 300 parts by mass of ZrO ₂ beads were pulverized and dispersed.

A near-infrared curing ink (hereinafter referred to as ink P) of Example 10 was prepared in the same manner as in Example 1 except that the microparticle dispersion liquid p was used instead of the microparticle dispersion liquid a.

A cured film of Example 10 (hereinafter referred to as cured film P) was obtained in the same manner as in Example 1 except that ink P was used instead of ink A.

The fine particle dispersion liquid p and the cured film P were evaluated in the same manner as in Example 1. Further, a hexagonal crystal structure was confirmed in the composite tungsten oxide fine particle sample.

The above results are shown in Tables 1 and 2.

[Comparative Example 1]

Except that the predetermined amounts of tungstic acid and cesium carbonate were measured in such a manner that the Molar ratio of W and Cs became 1: 0.15, the same operation as in Example 1 was performed to obtain Cs tungsten oxide fine particles (hereinafter referred to as fine particles j).

A dispersion liquid of fine particles j (hereinafter referred to as fine particle dispersion liquid j) was obtained in the same manner as in Example 1 except that fine particles j were used instead of fine particles a.

Next, in the same manner as in Example 1 except that the microparticle dispersion liquid j was used instead of the microparticle dispersion liquid a, a near-infrared curing ink of Comparative Example 1 (hereinafter referred to as ink J) was prepared.

A cured film of Comparative Example 1 (hereinafter referred to as cured film J) was obtained in the same manner as in Example 1 except that ink J was used instead of ink A.

The fine particle dispersion liquid j and the cured film J were evaluated in the same manner as in Example 1.

The above results are shown in Tables 1 and 2.

[Comparative Example 2]

A Cs tungsten oxide fine particle (hereinafter referred to as a fine particle) of Comparative Example 2 was obtained in the same manner as in Example 1 except that the predetermined amounts of tungstic acid and cesium carbonate were measured so that the molar ratio of W and Cs became 1: 0.39. k).

A dispersion liquid of fine particles k (hereinafter referred to as fine particle dispersion liquid k) was obtained in the same manner as in Example 1 except that fine particles k were used instead of fine particles a.

Next, in the same manner as in Example 1 except that the microparticle dispersion liquid k was used instead of the microparticle dispersion liquid a, a near-infrared curing ink of Comparative Example 2 (hereinafter referred to as ink K) was prepared.

A cured film of Comparative Example 2 (hereinafter referred to as cured film K) was obtained in the same manner as in Example 1 except that ink K was used instead of ink A.

The fine particle dispersion liquid k and the cured film K were evaluated in the same manner as in Example 1.

The above results are shown in Tables 1 and 2.

[Comparative Example 3]

Except that the existing amounts of tungstic acid and cesium carbonate were measured such that the molar ratio of W and Cs became 1: 0.23 and calcined at a temperature of 400 ° C for 5.5 hours, the same operation was performed as in Example 1 to obtain Comparative Example 3. Cs tungsten oxide fine particles (hereinafter referred to as fine particles 1).

Next, in the same manner as in Example 1 except that the microparticle dispersion liquid a was used instead of the microparticle dispersion liquid a, a near-infrared curing ink of Comparative Example 3 (hereinafter referred to as ink L) was prepared.

A cured film of Comparative Example 3 (hereinafter referred to as cured film L) was obtained in the same manner as in Example 1 except that ink L was used instead of ink A.

The fine particle dispersion liquid 1 and the cured film L were evaluated in the same manner as in Example 1.

The above results are shown in Tables 1 and 2.

[Comparative Example 4]

Except that the existing amounts of tungstic acid and cesium carbonate were measured such that the molar ratio of W and Cs was 1: 0.23, and calcined at 600 ° C for 5.5 hours, the rest were performed in the same manner as in Example 1 to obtain Comparative Example 4. Cs tungsten oxide fine particles (hereinafter referred to as fine particles m).

Next, 20 parts by mass of fine particles m, 65 parts by mass of methyl isobutyl ketone, and 15 parts by mass of an acrylic dispersant were mixed to prepare a mixture. This mixture was charged into a pigment shaker (manufactured by Asada Iron Works Co., Ltd.) and subjected to a dispersion treatment for 10 minutes to obtain a dispersion liquid of fine particles m (hereinafter referred to as fine particle dispersion liquid m).

Except for using microparticle dispersion liquid m instead of microparticle dispersion liquid a, Example 1 was performed in the same manner to prepare a near-infrared curing ink of Comparative Example 4 (hereinafter referred to as ink M).

A cured film of Comparative Example 4 (hereinafter referred to as cured film M) was obtained in the same manner as in Example 1 except that ink M was used instead of ink A.

The microparticle dispersion liquid m and the cured film M were evaluated in the same manner as in Example 1.

The above results are shown in Tables 1 and 2.

[Comparative Example 5]

20 parts by mass of fine particles a, 65 parts by mass of methyl isobutyl ketone, and 15 parts by mass of an acrylic dispersant were mixed to prepare a mixture. Fill this mixture until 0.3mm is added A pigment shaker (manufactured by Asada Iron Works) of ZrO ₂ beads was pulverized and dispersed for 50 minutes to obtain a fine particle dispersion liquid (hereinafter, referred to as a fine particle dispersion liquid n) of fine particles a. At this time, 0.3 mm was used with respect to 100 parts by mass of the mixture. 300 parts by mass of ZrO ₂ beads were pulverized and dispersed.

A near-infrared curable ink (hereinafter referred to as ink N) of Comparative Example 5 was prepared in the same manner as in Example 1 except that the microparticle dispersion liquid n was used instead of the microparticle dispersion liquid a.

A cured film of Comparative Example 5 (hereinafter referred to as cured film N) was obtained in the same manner as in Example 1 except that ink N was used instead of ink A.

The fine particle dispersion liquid n and the cured film N were evaluated in the same manner as in Example 1.

The above results are shown in Tables 1 and 2.

[Comparative Example 6]

20 parts by mass of fine particles m, 65 parts by mass of methyl isobutyl ketone, and 15 parts by mass of an acrylic dispersant were mixed to prepare a mixture. Fill this mixture until 0.3mm is added A pigment shaker (manufactured by Asada Iron Works) of ZrO2 beads was pulverized and dispersed for 4 hours to obtain a dispersion liquid of fine particles m (hereinafter referred to as fine particle dispersion liquid o). At this time, 0.3 mm was used with respect to 100 parts by mass of the mixture. 300 parts by mass of ZrO ₂ beads were pulverized and dispersed.

A near-infrared curing ink of Comparative Example 6 (hereinafter referred to as ink O) was prepared in the same manner as in Example 1 except that the microparticle dispersion liquid o was used instead of the microparticle dispersion liquid a.

A cured film of Comparative Example 6 (hereinafter referred to as cured film O) was obtained in the same manner as in Example 1 except that Ink O was used instead of Ink A.

The fine particle dispersion liquid o and the cured film O were evaluated in the same manner as in Example 1.

The above results are shown in Tables 1 and 2.

[to sum up]

From the results of Examples 1 to 10 and Comparative Examples 1 to 6 shown above, it was confirmed that the cured films of Examples 1 to 10 absorbed light in the near-infrared region with high efficiency and had high adhesion to the substrate.

In contrast, the cured films of Comparative Examples 1 to 6 all had insufficient near-infrared characteristics and had low adhesion to the substrate.

Claims (19)

A near-infrared hardening ink composition containing composite tungsten oxide particles with near-infrared absorbing ability and unhardened thermosetting resin; characterized in that the composite tungsten oxide particles have a crystal structure containing hexagonal crystals The composite tungsten oxide fine particles; the lattice constants of the above composite tungsten oxide fine particles are a-axis above 7.3850Å and below 7.4186Å, and c-axis is above 7.5600Å and below 7.6240Å; the average particle diameter of the above-mentioned composite tungsten oxide particles It is 100 nm or less. For example, the near-infrared hardening ink composition of claim 1, wherein the lattice constant of the composite tungsten oxide fine particles is a-axis of 7.4031 Å or more and 7.4111 Å or less, and a c-axis of 7.5891 Å or more and 7.6240 Å or less. The near-infrared hardening ink composition according to claim 1 or 2, wherein the average particle diameter of the composite tungsten oxide fine particles is 10 nm or more and 100 nm or less. The near-infrared hardening ink composition according to any one of claims 1 to 3, wherein a grain diameter of the composite tungsten oxide fine particles is 10 nm or more and 100 nm or less. The near-infrared curable ink composition according to any one of claims 1 to 4, further comprising a dispersant. The near-infrared curable ink composition according to any one of claims 1 to 5, further comprising a solvent. The near-infrared hardening ink composition according to any one of claims 1 to 6, wherein the composite tungsten oxide is of the general formula M _x W _y O _z (the M element is selected from the group consisting of H, He, an alkali metal, and an alkaline earth group) 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, Yb For elements, W is tungsten, O is oxygen, and 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0). The near-infrared hardening ink composition according to claim 7, wherein the composite tungsten oxide is composed of a composite tungsten oxide whose M element is one or more selected from Cs and Rb. The near-infrared hardening ink composition according to any one of claims 1 to 8, wherein at least a part of the surface of the composite tungsten oxide fine particles is composed of at least one selected from the group consisting of Si, Ti, Zr, and Al. The surface of the element is covered with a covering film. The near-infrared curable ink composition according to claim 9, wherein the surface coating film contains an oxygen atom. The near-infrared curable ink composition according to any one of claims 1 to 10, further comprising any one or more selected from the group consisting of an organic pigment, an inorganic pigment, and a dye. A near-infrared hardened film, characterized in that the near-infrared hardened ink composition according to any one of claims 1 to 11 is subjected to near-infrared irradiation and hardened. A photoforming method comprising applying a near-infrared curable ink composition according to any one of claims 1 to 11 to a base material to form a coating material, and irradiating the coating material with near-infrared light to harden the coating material. A method for manufacturing a near-infrared hardening ink composition, which is a method for manufacturing a near-infrared hardening ink composition containing near-infrared absorbing composite tungsten oxide particles, an unhardened thermosetting resin, a dispersant and a solvent; It is characterized in that the composite tungsten oxide fine particles are composite tungsten oxide fine particles containing a crystalline structure of hexagonal crystals; the composite tungsten oxide fine particles are based on a lattice constant of 7.3850Å and an a-axis. And 7.4186Å and below, and c-axis ranging from 7.5600Å to 7.6240Å; while maintaining the range of the above-mentioned lattice constant of the composite tungsten oxide fine particles, the pulverization is performed so that the average particle diameter becomes 100nm or less. Decentralized processing steps. The method for producing a near-infrared hardening ink composition according to claim 14, wherein the above composite tungsten oxide is of the general formula M _x W _y O _z z (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, Yb , W is tungsten, O is oxygen, and 0.001 ≦ x / y ≦ 1, 2.0 ≦ z / y ≦ 3.0). The method for producing a near-infrared hardening ink composition according to claim 14 or 15, wherein the composite tungsten oxide is composed of a composite tungsten oxide whose M element is one or more selected from Cs and Rb. The method for producing a near-infrared hardening ink composition according to any one of claims 14 to 16, wherein at least a part of the surface of the composite tungsten oxide fine particles is composed of any one of Si, Ti, Zr, and Al The surface of the above elements is covered with a coating film. The method for producing a near-infrared curable ink composition according to claim 17, wherein the surface coating film contains an oxygen atom. The method for producing a near-infrared curable ink composition according to any one of claims 14 to 18, wherein the near-infrared curable ink composition further contains at least one selected from the group consisting of an organic pigment, an inorganic pigment, and a dye.