JP7075713B2 - Dispersions, colored layers, colored films, colored substrates, colored combined substrates, and inks - Google Patents

Description

The present invention relates to a dispersion having no color tone such as reddish, bluish, greenish, and yellowish colors, a colored layer, a colored film, a colored base material, and a colored combination used for windows of transportation equipment such as automobiles and building materials. Regarding base material and ink.

Many of the windows of transportation equipment such as automobiles and building materials are transparent and have high transmittance of ultraviolet rays, visible rays and infrared rays. Therefore, for the purpose of preventing dazzling of vehicle passengers due to sunlight, improving the comfort inside and inside the vehicle, improving cooling efficiency and vehicle fuel efficiency, and protecting privacy by blocking the human line of sight, windows are not completely blocked from light. There is a demand in the market for a colored base material, a sticking film, and the like that appropriately reduce the transmittance of light.

In order to realize the above requirements, for example, a film colored with a black dye material such as aniline black, dark azo, perylene black, carbon black, or a film containing these dye materials in a hard coat layer or an adhesive layer is used. Many are commercially available.

Further, for example, Patent Document 1 describes a colored film in which at least one colored pressure-sensitive adhesive layer is provided on one surface of a transparent film, wherein the pressure-sensitive adhesive layer is a colorant composed of a pigment and a dispersant. A colored film colored by is disclosed. In the colored film, the coloring agent is a copper phthalocyanine pigment, an anthraquinone red pigment, or a disazo yellow pigment.

Japanese Unexamined Patent Publication No. 9-125081

Here, for example, the operator of the transportation equipment needs to look out from the window and accurately recognize various signals and traffic conditions. Therefore, a colored base material or a colored film having no color tone such as reddish, bluish, greenish, or yellowish is required for a colored base material or a colored film provided on a window of a transportation device.
In recent years, there has been a demand for colored substrates and colored films that do not have color tones such as redness, bluishness, greenness, and yellowness in fields such as construction, industrial fields, optical elements, and sunglasses, including the transportation equipment field. ing.
In the present invention, the colored base material having no color tone such as reddish, bluish, greenish, and yellowish is referred to as a "colored base material having a natural color tone" in the same manner as reddish and bluish. , A colored film having no color tone such as greenish color and yellowish color may be described as "a film having a natural color tone".

However, as a result of the study by the present inventors, the following problems have been found.
That is, the colored base material and the colored film according to the above-mentioned conventional technique cannot realize a natural color tone at a high level in a wavelength region having a low visible light transmittance. In addition, the weather resistance of the colored base material and the colored film is low.

Here, the present inventors have conducted research, and a colored substrate or a colored film having a natural color tone "absorbs", "shields", or "transmits" light of a specific wavelength in the wavelength region of visible light. I came up with the idea that there is nothing. In other words, in a colored substrate or colored film, by evenly "absorbing", "shielding" or "transmitting" light in the wavelength range of visible light, reddish, bluish and green in human vision. We thought that it would be a colored base material or a colored layer that does not sense color tones such as taste and yellowness.

For example, in a colored film in which a coloring base material, an adhesive, or a hard coat is colored with a black organic dye material such as aniline black according to a conventional technique, the black organic dye material uniformly illuminates the entire visible light region. Since it is not a pigment material that absorbs light, it has not been a colored base material having a natural color tone. Further, since the weather resistance of the black organic dye material is not sufficient, the optical characteristics deteriorate and the light shielding performance deteriorates after a very short period of use.

Further, for example, in a colored base material or a colored film in which a transparent base material such as a film or a board, an adhesive layer, or a hard coat is colored with carbon black, the absorption of the carbon black is on the short wavelength side and the long wavelength side of visible light. Because it was different from the above, it did not have a natural color tone.
Further, for example, in a colored substrate or a colored film colored with a highly weather-resistant colored pigment such as a phthalocyanine blue pigment, the phthalocyanine blue pigment absorbs only light in a part of the wavelength region of visible light. After all, it did not have a natural color tone.

From the above findings, it was considered to obtain a colored base material having a natural color tone by combining three or more kinds of colored pigments and colored dyes for color matching.
However, as a result of research by the present inventors, it has been extremely difficult to achieve an industrially stable color tone by toning three or more kinds of dyes. Further, if even one of the dyes used has a low weather resistance, there is a problem that the color tone of the toned dye changes due to the deterioration of the dye having the low weather resistance.

The present invention has been made under the above-mentioned circumstances, and the problem to be solved thereof is that a natural color tone can be realized by a combination of a small number of kinds of coloring materials, the weather resistance is high, and it is industrially feasible. It is an object of the present invention to provide a colored layer, a colored film, a colored base material, a colored combined base material, a dispersion used for producing these, and an ink.

The present inventors conducted research in order to solve the above-mentioned problems. Then, an ink containing titanium compound fine particles and carbon black fine particles in a predetermined weight ratio and dispersed in one or more solvents selected from an organic solvent and water was prepared. The dispersion, the colored layer, the colored film, the colored base material, and the colored combined base material produced by applying the ink are a combination of only two kinds of coloring materials, and are easy to carry out industrially. However, it was found that it is possible to achieve a specifically natural color tone in the transmitted color and the reflected color in the region where the visible light transmittance is low.

Specifically, the colored layer, the colored film, the colored base material, and the colored combined base material having the above-mentioned configurations are calculated based on JIS Z 8701: 1999 and JIS Z 8729: 2004 with a D65 light source and a 10-degree field of view. In the L * a * b * color tone value, the value of at least one of the transparent color coordinate or the reflected color coordinate, a * and b *, is the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 . It has been found that a color tone satisfying ≦ 3, more preferably a color tone satisfying the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2 can be realized.

The composition of the colored base material and the colored combined base material according to the present invention is as follows.
The colored base material has a structure in which a coating layer or an adhesive layer is provided on at least one surface of the base material, and at least one layer selected from the coating layer or the pressure-sensitive adhesive layer is a colored layer.
Further, the colored combined base material has a plurality of transparent base materials and one or more selected from a colored layer, a colored film, and a colored base material, and is selected from the colored layer, the colored film, and the colored base material. One or more of them have a configuration in which they are arranged between the plurality of transparent substrates.

The present inventors have described above as an ink containing a dispersion in which titanium compound fine particles and carbon black fine particles are dispersed in a medium, titanium compound fine particles, carbon black fine particles, and an organic solvent or water. It was also found that it is suitable as a dispersion and an ink for producing a dispersion, a colored base material, and a colored combined base material.

Furthermore, when the present inventors use at least one of titanium nitride fine particles, titanium oxide fine particles, and weakly reduced titanium oxide fine particles as the titanium compound described above, a dispersion having the above-mentioned constitution, a colored substrate, and coloring are used. It was found that a natural color tone can be realized especially in the laminated substrate and the ink.
Then, he came up with the idea that both the titanium compound fine particles and the carbon black fine particles are inorganic substances and have excellent weather resistance.

More interestingly, the present inventors have a colored base material having the above-mentioned structure, which has a lower illuminance transmittance than a colored base material such as a colored film manufactured by the prior art, and can also be used as a heat shield base material. It was found that it has high performance, and the present invention was completed.

That is, the first invention that solves the above-mentioned problems is
Titanium compound fine particles and carbon black fine particles are dispersed in the medium,
The titanium compound fine particles are one or more selected from titanium nitride fine particles, titanium oxide fine particles, and weakly reduced titanium oxide fine particles.
The average dispersed particle diameter of the titanium compound fine particles and the carbon black fine particles is 50 nm or less and 1 nm or more.
The weight ratio of the titanium compound fine particles to the carbon black fine particles is in the range of [titanium compound fine particles] / [carbon black fine particles] = 100: 10 to 100: 100.
When a colored layer is formed on a substrate and the total weight of the titanium compound fine particles and the carbon black compound fine particles contained per unit projected area is 0.05 g / m ² or more and 1.50 g / m ² or less. ,
The visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0.5% or more and 40% or less.
In the L * a * b * tint values calculated in the D65 light source and 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004, the values of the transmitted color coordinates a * and b * are expressed in the formula 0. ≤ ((a *) ² + (b *) ² ) ^0.5 ≤ 2 is a dispersion characterized by satisfying.
The second invention is
The third invention, which is the dispersion according to the first invention, further contains infrared-absorbing fine particles.
The second feature is that the infrared absorbing fine particles are one or more selected from tungsten oxide fine particles, composite tungsten oxide fine particles, borohydride fine particles, antimony-added tin oxide fine particles, and tin-added indium fine particles. The dispersion according to the invention .
The fourth invention is
The dispersion according to any one of the first to third inventions, wherein the medium is an inorganic binder and / or an organic binder.
The fifth invention is
The dispersion according to the fourth invention, wherein the organic binder is one or more selected from an ultraviolet curable resin, a thermosetting resin, an electron beam curable resin, a room temperature curable resin, and a thermoplastic resin. be.
The sixth invention is
Titanium compound fine particles and carbon black fine particles are dispersed in the medium,
The titanium compound fine particles are one or more selected from titanium nitride fine particles, titanium oxide fine particles, and weakly reduced titanium oxide fine particles.
The average dispersed particle diameter of the titanium compound fine particles and the carbon black fine particles is 50 nm or less and 1 nm or more.
A dispersion in which the weight ratio of the titanium compound fine particles to the carbon black fine particles is in the range of [titanium compound fine particles] / [carbon black fine particles] = 100: 10 to 100: 100 is formed on the substrate. It is a colored layer that is
The total weight of the titanium compound fine particles and the carbon black compound fine particles contained per unit projected area is 0.05 g / m ² or more and 1.50 g / m ² or less.
The visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0.5% or more and 40% or less.
In the L * a * b * tint values calculated in the D65 light source and 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004, the values of the transmitted color coordinates a * and b * are expressed in the formula 0. ≤ ((a *) ² + (b *) ² ) ^0.5 ≤ 2 is a colored layer characterized by satisfying.
The seventh invention is
The colored layer according to a sixth aspect of the invention, wherein the base material is a resin or glass.
The eighth invention is
Titanium compound fine particles and carbon black fine particles are dispersed in the medium,
The titanium compound fine particles are one or more selected from titanium nitride fine particles, titanium oxide fine particles, and weakly reduced titanium oxide fine particles.
The average dispersed particle diameter of the titanium compound fine particles and the carbon black fine particles is 50 nm or less and 1 nm or more.
A molded body of a dispersion in which the weight ratio of the titanium compound fine particles to the carbon black fine particles is in the range of [titanium compound fine particles] / [carbon black fine particles] = 100: 10 to 100: 100.
The molded body has a film-like, sheet-like, or board-like shape.
The total weight of the titanium compound fine particles and the carbon black compound fine particles contained per unit projected area is 0.05 g / m ² or more and 1.50 g / m ² or less.
The visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0.5% or more and 40% or less.
In the L * a * b * tint values calculated in the D65 light source and 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004, the values of the transmitted color coordinates a * and b * are expressed in the formula 0. ≦ ((a *) ² + (b *) ² ) A colored film characterized by satisfying ^0.5 ≦ 2.
The ninth invention is
The colored film according to the eighth aspect of the invention, wherein the colored film contains a thermoplastic resin.
The tenth invention is
One or more selected from the colored layer according to the sixth or seventh invention and the colored film according to the eighth or ninth invention is provided on the transparent substrate. It is a colored base material to be used.
The eleventh invention is
The visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0.5% or more and 40% or less.
In the L * a * b * tint values calculated in the D65 light source and 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004, the values of the transmitted color coordinates a * and b * are expressed in the formula 0. ≤ ((a *) ² + (b *) ² ) The colored substrate according to the tenth invention, which is characterized by satisfying ^0.5 ≤ 2.
The twelfth invention is
The colored substrate according to the tenth or eleventh invention request, wherein the transparent substrate is a resin or glass.
The thirteenth invention is
Any one selected from the colored layer according to the sixth or seventh invention, the colored film according to the eighth or ninth invention, and the colored substrate according to any one of the tenth to twelfth inventions. The seeds or more are colored combined base materials characterized in that they are provided between a plurality of transparent base materials.
The fourteenth invention is
The visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0.5% or more and 40% or less.
In the L * a * b * tint values calculated in the D65 light source and 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004, the values of the transmitted color coordinates a * and b * are expressed in the formula 0. ≤ ((a *) ² + (b *) ² ) The colored combined substrate according to the thirteenth invention, which is characterized by satisfying ^0.5 ≤ 2.
The fifteenth invention is
The colored combined substrate according to the thirteenth or fourteenth invention, wherein the transparent substrate is a resin or glass.
The sixteenth invention is
An ink containing titanium compound fine particles, carbon black fine particles, and one or more selected from an organic solvent or water.
The titanium compound fine particles are one or more selected from titanium nitride fine particles, titanium oxide fine particles, and weakly reduced titanium oxide fine particles.
The average dispersed particle diameter of the titanium compound fine particles and the carbon black fine particles is 50 nm or less and 1 nm or more.
The weight ratio of the titanium compound fine particles contained in the ink to the carbon black fine particles is in the range of [titanium compound fine particles] / [carbon black fine particles] = 100: 10 to 100: 100.
Using the ink, a colored layer on a transparent substrate in which the total weight of the titanium compound fine particles and the carbon black compound fine particles contained per unit projected area is 0.05 g / m ² or more and 1.50 g / m ² or less. JIS Z 8701: 1999 and JIS when the visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0.5% or more and 40% or less in the optical characteristics of the colored substrate formed in In the L * a * b * tint values calculated in the D65 light source and 10-degree field of view based on Z 8729: 2004, the values of the transmitted color coordinates a * and b * are expressed by the formula 0 ≦ ((a *) ² ). + (B *) ² ) An ink characterized by satisfying ^0.5 ≦ 2.
The seventeenth invention is
The ink according to the sixteenth invention, which further contains infrared-absorbing fine particles.
The eighteenth invention is
The seventeenth characteristic is that the infrared absorbing fine particles are one or more selected from tungsten oxide fine particles, composite tungsten oxide fine particles, borohydride fine particles, antimony-added tin oxide fine particles, and tin-added indium fine particles. The ink according to the invention .

The colored layer, the colored film, the colored base material, and the colored combined base material according to the present invention produced by using the dispersion and the ink according to the present invention have a natural color tone even though they are a combination of two kinds of coloring materials. It has high weather resistance and is industrially easy to implement.

It is a transmission curve of the colored film and the base film measured in Example 21, Comparative Examples 1 to 4, and Reference Example 1. From the colored film and substrate film transmission curves measured in Example 21, Comparative Examples 1 to 4, and Reference Example 1, the transmission curve is expanded in the vicinity of the wavelength region of visible light and in the vicinity of the low transmittance region.

Hereinafter, embodiments of the present invention will be described in detail.
The dispersion according to the present invention is a concept that refers to a state in which at least titanium compound fine particles and carbon black fine particles are dispersed in a medium. Here, the medium is a dispersion medium such as a solid or a gel, and specifically, an inorganic binder and / or an organic binder can be used. Examples of the inorganic binder include silicone resins, and the organic binder may be one or more selected from ultraviolet curable resin, thermosetting resin, electron beam curable resin, room temperature curable resin, and thermoplastic resin. preferable.
And, preferably, it is a concept which refers to a state in which at least titanium compound fine particles and carbon black fine particles are dispersed in a solid medium.

When the dispersion is formed as a coating layer, an adhesive layer, etc. on at least one surface of the base material and constitutes the colored base material according to the present invention, the dispersion is referred to as a "colored layer". In some cases.
Further, when the dispersion is contained in the resin and the resin is molded into a film shape, a sheet shape, a board shape, or the like, the molded body may be referred to as a “colored film”.
On the other hand, when the dispersion is in the form of powder, the powder may be described as "dispersion powder".
Further, if the dispersion is in the form of pellets, the pellet may be referred to as a "masterbatch".

Next, the ink according to the present invention is
(A) A dispersion liquid in which titanium compound fine particles and / or carbon black fine particles are dispersed in a solvent,
(B) A coating liquid that can be used for forming a coating layer by adding a coating resin to the dispersion liquid according to (a) described above.
(C) A coating liquid that can be used for forming a pressure-sensitive adhesive layer by adding a pressure-sensitive adhesive to the dispersion liquid according to (a) described above.
The above is the concept including the dispersion liquid and the coating liquid.
When distinguishing the above concepts, (a) is referred to as "dispersion liquid" or "fine particle dispersion liquid", (b) is referred to as "coating ink", and (c) is referred to as "adhesive layer forming liquid". May be stated.

The above-mentioned colored layer according to the present invention contains titanium compound fine particles such as a coating layer such as a hard coat manufactured by using the above-mentioned ink and a pressure-sensitive adhesive layer manufactured by using the above-mentioned ink, and carbon black fine particles. It is a concept that includes a colored layer.

Next, the colored substrate according to the present invention is in the form of having at least one surface of the transparent substrate having the above-mentioned coating layer, one or more colored layers selected from the pressure-sensitive adhesive layer, and / or the above-mentioned colored film. .. The concept is that at least one layer of the coating layer or the pressure-sensitive adhesive layer contains titanium compound fine particles, and at least one layer of the coating layer or the pressure-sensitive adhesive layer contains carbon black fine particles.

The colored laminated base material according to the present invention is a concept indicating a laminated base material in which one or more selected from the above-mentioned colored layer, colored film, and colored base material is present between a plurality of transparent base materials. ..

Hereinafter, [1] an ink, a dispersion, a colored base material and a component constituting the colored base material, [2] an ink, a dispersion powder and a master batch form and a method for producing the same, and [3] a colored layer, according to the present invention. The colored base material, the colored film, the colored laminated base material, and the method for producing the same will be described in detail.

[1] As a component constituting an ink, a dispersion, a colored layer, a colored film, a colored base material and a colored laminated base material, as a component constituting an ink, a dispersion, a colored layer, a colored film, a colored base material and a colored laminated base material. , (1) Titanium compound fine particles, (2) Carbon black fine particles, (3) Solvent, (4) Dispersant, (5) Ink-absorbing compound, (6) Coating resin, (7) Adhesive, (8) Others Additives, (9) transparent substrate, and (10) thermoplastic resin will be described in detail in this order.

(1) Titanium compound fine particles As the titanium compound fine particles according to the present invention, those having a strong coloring in the visible light region and exhibiting a bluish purple color when used alone as a fine particle dispersion can be preferably used. Specifically, titanium nitride fine particles, titanium oxide fine particles, and weakly reduced titanium oxide (TiO _2-x ) fine particles can be mentioned as fine particles having excellent optical properties from the above viewpoint.

The titanium nitride fine particles have a chemical formula represented by TiN, but can be applied even if the molar ratio of Ti to N is in the range of 1: 1 to ± 20% and is deviated.

Here, the titanium nitride fine particles are fine particles corresponding to those in which a part of N of the titanium nitride fine particles described above is replaced with O. Even in the titanium oxide fine particles, the molar ratio of Ti and N + O varies in the range of 1: 1 to ± 20%. As a result, even titanium oxide fine particles whose molar ratio deviates from 1: 1 can be applied.

The weakly reduced titanium oxide fine particles are the fine particles of weakly reduced titanium oxide (TIM _2-x ) obtained by the weak reduction treatment of titanium oxide (TiO ₂ ). As a specific composition, in the composition formula represented by TiO _2-x , those in the range of approximately 0.02 ≦ x ≦ 0.8 can be mentioned. More specific compositions include dititanium trioxide (Ti ₂ O ₃ ), tetratitanium heptaoxide (Ti ₄ O ₇ ), mixed crystals thereof, or mixtures thereof.
As the above-mentioned weak reduction treatment, a known treatment method such as a firing treatment in a reducing atmosphere such as hydrogen or ammonia, or a firing treatment mixed with CaH ₂ can be used.

As described above, when the particle size of the titanium compound fine particles such as titanium oxide fine particles, titanium oxide fine particles, and weakly reduced titanium oxide fine particles is 100 nm or less, preferably 50 nm or less, and most preferably 40 nm or less, the titanium compound fine particles are visible light. It does not cause the scattering of light in the region, and clear transparency can be obtained in the colored layer and the colored substrate described later.
On the other hand, if the particle size is 1 nm or more, the production is easy.
Further, all of these titanium compound fine particles are inorganic compounds and have high weather resistance.

(2) Carbon black fine particles As the carbon black fine particles according to the present invention, when the nitrogen adsorption specific surface area (BET value) is large and the particle diameter is small, the hiding power is strong and the dispersibility is improved, which is preferable. From this point of view, the particle size of the carbon black fine particles is preferably 100 nm or less, preferably 50 nm or less, and more preferably 30 nm or less.
On the other hand, if the particle size is 1 nm or more, the production is easy.
Then, in order to improve the dispersibility of the carbon black fine particles, it is also preferable to perform a surface modification treatment on the carbon black fine particles. The surface modification treatment method for improving the dispersibility can be arbitrarily selected from known methods, and examples thereof include plasma treatment and coating treatment with a resin.
Further, the carbon black fine particles are inorganic compounds and have high weather resistance.

(3) Solvent In the ink according to the present invention, the solvent used as a dispersion medium for the titanium compound fine particles and the carbon black fine particles is not particularly limited. The solvent can be selected according to the resin to be blended in the ink. Specifically, general solvents such as water, alcohol, ether, ester, ketone, aromatic compound, etc. can be used. Moreover, one or more solvents selected from these solvents can be used.
If necessary, an acid or an alkali may be added to the solvent to adjust the pH of the solvent.

(4) Dispersant The dispersant according to the present invention comprises the above-mentioned titanium compound fine particles or carbon black fine particles according to the present invention in the above-mentioned solvent, in the resin used for the coloring film described later, in the coating resin, or the pressure-sensitive adhesive. It is used to evenly disperse into it.
As the dispersant, for example, a phosphoric acid ester compound, a polymer-based dispersant, a silane-based coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, or the like can be preferably used. Examples of the polymer-based dispersant include an acrylic-based polymer dispersant, a urethane-based polymer dispersant, an acrylic block copolymer-based polymer dispersant, a polyether-based dispersant, and a polyester-based polymer dispersant. .. The dispersant is not limited to these, and various dispersants can be used.

However, the dispersant is preferably a dispersant having an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. These functional groups are adsorbed on the surface of the titanium compound fine particles and the carbon black fine particles to suppress the aggregation of the fine particles, and the fine particles are uniformly distributed in the solvent, the colored film, the coating resin, or the adhesive. It has the effect of dispersing.

The amount of the dispersant added is preferably in the range of 10 parts by weight to 2000 parts by weight, more preferably in the range of 30 parts by weight to 1000 parts by weight with respect to 100 parts by weight of the fine particles. When the amount of the dispersant added is within the above range, the fine particles are uniformly dispersed in the solvent, the coating resin, the thermoplastic resin, and the adhesive, and are formed on the colored film and finally on the base film. This is because it does not adversely affect the physical properties of the coating layer, the transparent base material, and the pressure-sensitive adhesive layer.

(5) Infrared Absorbent Compound As described above, the ink, dispersion, colored layer, colored film, colored base material and colored combined base material according to the present invention have sufficient absorption capacity even in the near infrared region. It also functions as a heat-shielding ink, a heat-shielding dispersion, a heat-shielding laminated base material, and a heat-shielding base material.
However, for the purpose of further improving the absorption capacity of near-infrared rays, an infrared-absorbing compound having a stronger absorption in the near-infrared region is applied to an ink, a dispersion, a colored layer, a colored film, a colored base material, and a colored combined base material. , Further may be added. The infrared-absorbing compound is roughly classified into an infrared-absorbing organic compound and an inorganic infrared-absorbing fine particle. Hereinafter, the infrared-absorbing organic compound and the inorganic infrared-absorbing fine particles will be described.

(I) Infrared-absorbing organic compounds Examples of the infrared-absorbing organic compounds used for the above-mentioned purposes include phthalocyanine compounds, naphthalocyanine compounds, imonium compounds, diimonium compounds, polymethine compounds, diphenylmethane compounds, triphenylmethane compounds, quinone compounds, and azo. Compounds, pentadiene compounds, azomethine compounds, squarylium compounds, organic metal complexes, cyanine compounds and the like can be used.

(Ii) Infrared Absorbing Fine Particles Examples of the inorganic infrared absorbing fine particles include tungsten oxide fine particles, composite tungsten oxide fine particles, boride fine particles, antimony-added tin oxide fine particles, and tin-added indium oxide fine particles. Further, examples of the composite tungsten oxide fine particles include cesium-added tungsten oxide fine particles and rubidium-added tungsten oxide fine particles.

Further, the composite tungsten oxide fine particles, the tin-added tin oxide fine particles, and the tin-added indium oxide fine particles have a concentration sufficient to significantly absorb near infrared rays, and the ink, dispersion, colored layer, and colored film according to the present invention. Even when added to a colored film, a colored base material, and a colored combined base material, these colors are not significantly affected and are preferable.

When the inorganic infrared-absorbing fine particles are added to the ink, dispersion, colored layer, colored film, colored film, colored base material and colored combined base material according to the present invention at a concentration sufficient to absorb near infrared rays significantly. However, it is preferable because it has excellent transparency of visible light and also has excellent weather resistance even when used as a colored board or a colored film in an outdoor or harsh environment similar to that outdoors.

The inorganic infrared-absorbing fine particles can be contained in the ink, dispersion, colored layer, colored film, colored film, colored base material and colored combined base material according to the present invention by a known method. For example, a composition in which infrared-absorbing fine particles, a solvent, and a dispersant, if necessary, are mixed is subjected to a dispersion treatment to form ink. The ink is added to the ink of the titanium compound fine particles and the carbon black fine particles according to the present invention to form a mixed ink, and the mixed ink is used to disperse the ink in the resin constituting the colored base material and coat the colored base material. The treatment and the pressure-sensitive adhesive layer forming treatment can be performed.

(6) Coating resin As the coating resin used for forming the coating layer, for example, an ultraviolet curable resin, a thermosetting resin, an electron beam curable resin, a room temperature curable resin, a thermoplastic resin, or the like can be selected according to the purpose. can. Above all, it is preferable to use an ultraviolet curable resin from the viewpoints of hardness, smoothness, dispersibility of fine particles, simplicity of process, and the like.

The ultraviolet curable resin can be used without particular limitation as long as it forms a transparent resin composition by curing, and examples thereof include silicone resin, epoxy resin, vinyl ester resin, acrylic resin, and allyl ester resin. .. Among them, an acrylic resin can be preferably used from the viewpoints of hardness, smoothness, transparency, and the like.

(7) Adhesive As the adhesive used for forming the adhesive layer, for example, an adhesive containing a photocurable or thermosetting resin as a main component can be used. The pressure-sensitive adhesive is preferably one having durability against ultraviolet rays, and preferably an acrylic pressure-sensitive adhesive or a silicone-based pressure-sensitive adhesive. Further, an acrylic pressure-sensitive adhesive is preferable from the viewpoint of adhesive properties, cost, and the like. There are solvent-based and emulsion-based acrylic pressure-sensitive adhesives, but solvent-based adhesives are preferable from the viewpoint of easy control of peel strength. When a solution-polymerized polymer is used as the acrylic solvent-based pressure-sensitive adhesive, known acrylic monomers can be used.

(8) Other Additives In the ink, dispersion, colored layer, colored film, colored film, colored base material and colored combined base material according to the present invention, various additives may be added as necessary. good. For example, by adding an ultraviolet shielding agent or HALS, it is possible to prevent ultraviolet deterioration of a colored layer, a colored film, and a colored film, and in addition, ultraviolet rays contained in sunlight can be applied to a colored base material, a colored combined base material, a colored film, and a colored layer. It is possible to prevent the invasion of the inside of the vehicle or the room through the colored film and cause light deterioration to the human skin, the inside of the vehicle, the furniture in the room, and the like.
Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, cerium oxide fine particles, zinc oxide fine particles, titanium oxide fine particles and the like.

Further, for example, by adding an antioxidant, deterioration of the colored substrate, the colored layer, and the colored film can be prevented. Further, for example, by adding a color tone adjusting agent such as a pigment fine particle dispersion or a dye, the color tone can be finely adjusted as long as the colored substrate or the colored layer maintains a natural color tone.

With respect to these additives, the colored layer and each layer of the colored base material other than the colored layer, for example, a hard code layer, a transparent base material, and an adhesive, may be used in various forms depending on the effect and desired of the additive. It can be contained in more than one layer selected from layers and the like.

(9) Transparent Base Material As the transparent base material used as the base material for the colored base material according to the present invention, a colorless and transparent base material that is transparent to visible light and has little scattering is preferable. Specifically, a base material selected from glass, a resin board, and a resin film is suitable. When the base material is a resin board or a resin film, the types of resin are specifically polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, and ethylene-vinyl acetate co-weight. Examples thereof include a coalesced resin, a polyester resin, a fluororesin, a polycarbonate resin, and an acrylic resin. Among them, when the base material is a resin film, a polyester resin is preferable, and a polyethylene terephthalate resin is particularly preferable.

When the transparent substrate is used, the surface thereof may be surface-treated for the purpose of improving the bondability with the resin binder, and typical treatment methods thereof are corona surface treatment, plasma treatment, and sputtering. Discharge treatment such as treatment, flame treatment, metallic sodium treatment, primer layer coating treatment and the like can be mentioned.

The transparent base material for arranging the colored layer, the colored film, and the colored base material between the plurality of transparent base materials or sandwiching the colored base material between the plurality of transparent base materials to form a colored laminated base material is glass. Is preferable.

(10) Thermoplastic Resin The dispersion according to the present invention can take the form of a colored film such as a sheet, a board, or a film by further containing a thermoplastic resin and molding the dispersion.
The thermoplastic resin contained in the colored film is preferably a colorless and transparent resin that is transparent to visible light and has little scattering. Specifically, polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin, polyester resin, fluororesin, ionomer resin, polycarbonate resin, acrylic. Examples include resin.

[2] Ink, Dispersed Powder and Masterbatch Form and Method for Producing the Ink (1) Ink Form and (2) Ink Manufacturing Method are described below to form a dispersion (3) Dispersed Powder and Master. The form of the batch and (4) the method for producing the dispersed powder and the masterbatch will be described.

(1) Ink Form The ink according to the present invention contains at least titanium compound fine particles, carbon black fine particles and a solvent, and further contains a dispersant, an infrared absorbing compound, a coating resin, an adhesive and other additives, if desired. contains.

By incorporating a coating resin or an adhesive into the ink according to the present invention to form a mixture, the mixture can be used for forming a colored layer.
For example, a coating ink containing titanium compound fine particles, carbon black fine particles, and a coating resin in the ink can be used for forming a coating layer of a colored base material.
On the other hand, for example, an ink containing titanium compound fine particles, carbon black fine particles, and a pressure-sensitive adhesive in the ink can be used as the pressure-sensitive adhesive layer forming liquid.

The ink according to the present invention has the optical properties of JIS Z 8701: 1999 and JIS Z 8729: 2004 obtained by forming a coating layer or an adhesive layer on a transparent base material using the ink. In the L * a * b * tint values calculated in the D65 light source and 10-degree field based on the above, the values of at least one of the transmitted color coordinates or the reflected color coordinates are a * and b * in the equation 0 ≦ ((a). *) ² + (b *) ² ) It contains titanium compound fine particles and carbon black fine particles in a ratio satisfying ^0.5 ≤ 3.
Specifically, when the weight ratio of the titanium compound fine particles contained in the ink to the carbon black fine particles is in the range of [titanium compound fine particles] / [carbon black fine particles] = 100: 10 to 100: 100. A colored substrate having a coating layer and / or a pressure-sensitive adhesive layer formed on a transparent substrate using the ink according to the present invention can satisfy the above-mentioned optical properties.

On the other hand, since the amount of titanium compound fine particles is smaller than the above-mentioned value of [titanium compound fine particles] / [carbon black fine particles] = 100: 10, the color tone of the colored base material is from gray to blue, which shows a natural color tone. You can avoid getting close to bluish purple. As a result, 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 3 and it becomes easy to satisfy the above-mentioned optical characteristics.
On the other hand, since the amount of carbon black fine particles is smaller than the value of the above-mentioned [titanium compound fine particles] / [carbon black fine particles] = 100: 100 weight ratio, the color tone of the colored base material changes from gray showing a natural color tone to brown. You can avoid getting close to it. As a result, 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 3 and it becomes easy to satisfy the above-mentioned optical characteristics.

In particular, an ink containing titanium compound fine particles and carbon black fine particles is used on a transparent substrate at a ratio satisfying the formula 0 ≤ ((a *) ² + (b *) ² ) ^0.5 ≤ 2. The optical properties of the colored substrate obtained by forming the coating layer or the pressure-sensitive adhesive layer are preferable because a more natural color tone can be realized.
Further, since the ink according to the present invention is an inorganic compound in both the titanium compound fine particles and the carbon black fine particles, it has high weather resistance.

Here, the optical properties of the colored substrate obtained by forming the coating layer or the pressure-sensitive adhesive layer on the transparent substrate using the ink according to the present invention are D65 based on JIS Z 8701: 1999 and JIS Z 8729: 2004. In the L * a * b * tint values calculated in the light source / 10-degree field, the values of at least one of the transmitted color coordinates or the reflected color coordinates are the formula 0 ≦ ((a *) ² +. (B *) ² ) The significance of satisfying ^0.5 ≤ 3, more preferably equation 0 ≤ ((a *) ² + (b *) ² ) ^0.5 ≤ 2 will be described.
The significance of the optical characteristics is the same for the optical characteristics of the colored layer and the colored substrate according to the present invention, which will be described later.

When the sample to be measured has color tones L ^* , a ^* , b ^* with respect to a standard sample having a predetermined color tone L ^* ₀ , a ^* ₀ , b ^* ₀ , it depends on the observer's skill level and color range. Although it may happen, the color difference of the measurement sample specified in JIS Z 8730: 2009 ΔE = ((ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ) ^1/2 = ((L ^* -L ^* ) ₀ ) ² + (a ^* -a ^* ₀ ) ² + (b ^* -b ^* ₀ ) ² ) When the value of ^1/2 is 0 or more and 3 or less, the difference in color tone between the standard sample and the sample to be measured is visually observed. It is difficult to distinguish by. In particular, if the color difference ΔE is 0 or more and 2 or less, it is more difficult to discriminate.
On the other hand, when the standard sample has an ideal gray color and has the same brightness as the sample to be measured, that is, the standard sample has L ^* ₀ = L ^* , a ^* ₀ = 0 and b ^* ₀ = 0. When is satisfied at the same time, the color difference of the sample to be measured with respect to the standard sample is calculated by ΔE = ((a ^* ) ² + (b ^* ) ² ) ^1/2 .
Therefore, when the color difference of the sample to be measured with respect to the standard sample having the ideal gray color tone satisfies the formula 0 ≤ ((a ^* ) ² + (b ^* ) ² ) ^1/2 ≤ 3, the ideal gray color is obtained. It is difficult to visually discriminate the difference in color tone between the standard sample having a color tone and the sample to be measured. When the relation of equation 0 ≦ ((a ^* ) ² + (b ^* ) ² ) ^1/2 ≦ 2 is satisfied, it is further difficult to discriminate.
As a result, by using the ink according to the present invention, it is possible to produce a colored layer or a colored base material having a natural color tone.

(2) Ink Production Method The ink according to the present invention can be produced by a known method.
At the time of this production, the ink according to the present invention can be produced by adding titanium compound fine particles and carbon black fine particles in a predetermined ratio to a solvent which is a liquid medium and simultaneously performing dispersion treatment on both fine particles. You can. Further, the ink according to the present invention is obtained by producing a dispersion liquid of titanium compound fine particles and a dispersion liquid of carbon black fine particles by separate dispersion treatments, and then mixing the two types of dispersion liquids at a predetermined ratio. May be manufactured.
The method of the dispersion treatment is not particularly limited as long as the titanium compound fine particles and / or the carbon black fine particles are uniformly dispersed in the liquid medium. For example, a bead mill, a ball mill, a sand mill, an ultrasonic dispersion, or the like can be used.

When the titanium compound fine particles and / or carbon black fine particles are added to the liquid medium and subjected to the dispersion treatment, an appropriate amount of a dispersant, a coupling agent, a surfactant or the like can be added as desired.

The above-mentioned infrared absorbing compound, coating resin, pressure-sensitive agent, and other additives may be added before the dispersion treatment of the titanium compound fine particles and / or the carbon black fine particles, or may be added after the dispersion treatment. ..
However, when inorganic infrared-absorbing fine particles are used as the infrared-absorbing compound, or when inorganic ultraviolet-absorbing fine particles are used as the ultraviolet absorber, a dispersion of these fine particles is prepared in advance, and the dispersion is used. , It is preferable to add it to the ink according to the present invention.
Further, when the coating resin or the pressure-sensitive adhesive is added before the dispersion treatment of the titanium compound fine particles and / or the carbon black fine particles, the viscosity of the liquid may increase in the dispersion treatment step and the dispersion efficiency may decrease. Therefore, it is preferable to add the coating resin or the pressure-sensitive adhesive to the dispersion liquid after the titanium compound fine particles and / or the carbon black fine particles are dispersed.

(3) Dispersed Powder and Masterbatch Form The dispersion according to the present invention contains at least titanium compound fine particles, carbon black fine particles and a dispersant. The dispersed powder has a powdery form, and the masterbatch has a pellet-like form.

By mixing the dispersed powder and the masterbatch according to the present invention with a thermoplastic resin, the mixture can be used for forming a colored film having a sheet-like, board-like or film-like form.

The dispersed powder and masterbatch according to the present invention are in the form of a sheet, a film or a board obtained by dispersing titanium compound fine particles and carbon black fine particles in a thermoplastic resin using the dispersed powder and the masterbatch. The optical characteristics of the colored film having a morphology can be considered in the same manner as the above-mentioned ink.

(4) Method for Producing Dispersed Powder and Masterbatch The dispersed powder and masterbatch according to the present invention can be produced by a known method.
For example, by removing volatile components such as an organic solvent from the above-mentioned dispersion liquid, it is possible to obtain a dispersion powder which is a powdery dispersion in which titanium compound fine particles and carbon black fine particles are dispersed at a high concentration in the dispersant. .. The method for removing the volatile components is not particularly limited, but for example, a method of drying the dispersion under reduced pressure can be preferably used.

Specifically, the dispersion is dried under reduced pressure while stirring to separate the dispersion from the volatile components. Examples of the apparatus used for the vacuum drying include a vacuum stirring type dryer, but the apparatus is not particularly limited as long as it has the above-mentioned function. Further, the pressure value at the time of vacuum drying is not particularly limited and can be appropriately selected.
By using the vacuum drying method when removing the volatile components from the dispersion liquid, the efficiency of removing the solvent from the mixture can be improved. Further, since the dispersion is not exposed to high temperature for a long time, it is preferable that the titanium compound fine particles and carbon black fine particles dispersed in the dispersion do not aggregate. Furthermore, it is easy to recover the evaporated solvent, which is preferable from the viewpoint of environmental consideration.
Further, by dispersing the dispersed powder in a resin and molding the resin into pellets, a pellet-shaped dispersion, that is, a masterbatch can be obtained.

In the obtained dispersed powder and masterbatch, the residual solvent is preferably 5% by mass or less. This is because if the residual solvent is 5% by mass or less, bubbles are not generated when the dispersed powder and the masterbatch are processed into, for example, a colored film described later, and the appearance and optical characteristics are kept good. Because.

[3] Colored layer, colored base material, colored film, colored combined base material, and method for manufacturing the same. , (3) The form of the colored film and the colored laminated base material, (4) the colored layer and the method for producing the colored base material, and (5) the method for producing the colored film and the colored combined base material will be described.

(1) Form of Colored Layer The colored layer according to the present invention is a colored layer containing at least titanium compound fine particles and carbon black fine particles, and is a D65 light source at 10 degrees based on JIS Z 8701: 1999 and JIS Z 8729: 2004. In the L * a * b * tint values calculated in the visual field, the values of at least one of the transmitted color coordinates or the reflected color coordinates, a * and b *, are expressed by the formula 0 ≦ ((a *) ² + (b *). ) ² ) It is characterized in that ^0.5 ≤ 3 is satisfied.

When the colored base material according to the present invention is produced using the colored layer of the present invention, the visible light transmittance calculated by JIS R 3106: 1998 is preferably 0.2% or more and 60% or less. This is because if the visible light transmittance is 0.2% or more, the visibility through the colored substrate can be guaranteed. If it is 60% or less, the transmittance of the colored base material for human visual sensitivity becomes appropriate, and the role of the colored base material is to prevent dazzling of vehicle passengers due to sunlight and to make the interior and interior of the vehicle comfortable. This is because the effects of improving the performance, improving the cooling efficiency and the fuel efficiency of the automobile, and protecting the privacy by blocking the human line of sight can be guaranteed.
From this point of view, it is more preferable that the visible light transmittance of the colored substrate is 0.5% or more and 40% or less.

When the colored layer and ink according to the present invention are used, for example, in a black matrix formed between pixels of a display, the total weight of the titanium compound fine particles and the carbon black fine particles per unit projected area is increased by increasing the total weight. The visible light transmittance of the colored layer can be adjusted to 0% or more and less than 0.2%.
The colored layer has substantially no visible light transmission, while the reflected color satisfies ΔE = ((a *) ² + (b *) ² ) ^0.5 ≦ 3, preferably ΔE = (((a *) 2 + (b *) 2) 0.5 ≦ 3. a *) ² + (b *) ² ) A colored layer having a natural color tone that satisfies ^0.5 ≤ 2.

By forming the colored layer on an arbitrary base material such as glass, a resin sheet, a resin film, etc. using the ink, a coating film having a deep black color and a natural color tone can be obtained. That is, the ink can be used as a paint or the like, and the colored layer can be used as a black matrix or the like formed between pixels of a display.

Even in a colored layer in which the visible light transmittance is adjusted to 0% or more and less than 0.2%, the optical characteristics thereof are JIS R 3106: 1998, as in the colored layer having a visible light transmittance of 0.2% or more and 60% or less. The visible light transmittance calculated in 1 is 0% or more and 60% or less, and the L * a * b * tint calculated in the D65 light source and 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004. In terms of values, at a ratio such that at least one of the transparent color coordinates or the reflected color coordinates, a * and b *, satisfies the equation 0 ≤ ((a *) ² + (b *) ² ) ^0.5 ≤ 3. , Titanium compound fine particles and carbon black fine particles are contained.
Further, in the colored layer which is the dispersion according to the present invention, the total weight of the titanium compound fine particles and the carbon black compound fine particles contained per unit projected area is 0.05 g / m ² or more and 1.50 g / m ² or less. Is preferable.

Specifically, the weight ratio of the titanium compound fine particles contained in the coating layer or the pressure-sensitive adhesive layer, which is the dispersion according to the present invention and is also the coloring layer, to the carbon black fine particles is [titanium compound fine particles] / [carbon. By having less titanium compound fine particles than the value of [black fine particles] = 100: 10, it is possible to avoid shifting the color of the colored base material from gray, which shows a natural color tone, to blue to bluish purple. As a result, ΔE = ((a *)) ² + (b *) ² ) ^0.5 ≦ 3, and it becomes easy to satisfy the above-mentioned optical characteristics.
On the other hand, since the amount of carbon black fine particles is smaller than the value of the above-mentioned [titanium compound fine particles] / [carbon black fine particles] = 100: 100 weight ratio, the color tone of the colored base material changes from gray showing a natural color tone to brown. You can avoid getting close to it. As a result, ΔE = ((a *) ² + (b *) ² ) ^0.5 ≦ 3 and it becomes easy to satisfy the above-mentioned optical characteristics.
In particular, a more natural color tone is realized by containing titanium compound fine particles and carbon black fine particles in a ratio that satisfies the formula 0 ≤ ((a *) ² + (b *) ² ) ^0.5 ≤ 2. Can be, and is particularly preferable.

In addition to the above-mentioned applications such as paints, black matrices, and colored base materials, the colored layer according to the present invention includes, for example, sunglasses, laser protective goggles, dimming filters and ND filters as optical elements, light-shielding films for agriculture, and foods. It can also be applied to protective films for use.
Further, since the colored layer according to the present invention is an inorganic compound in both the titanium compound fine particles and the carbon black fine particles, it has high weather resistance.

(2) Form of Colored Base Material The colored base material according to the present invention has a transparent base material containing at least titanium compound fine particles and carbon black fine particles, or has a coating layer or a pressure-sensitive adhesive layer on at least one surface of the transparent base material. It is a colored base material. Then, at least one layer of the coating layer or the pressure-sensitive adhesive layer is a colored layer, and the colored base material is also calculated based on JIS Z 8701: 1999 and JIS Z 8729: 2004 with a D65 light source and a 10-degree field of view. In the L * a * b * tint value, the value of at least one of the transparent color coordinate or the reflected color coordinate, a * and b *, is the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 . It is characterized in that ≦ 3 is satisfied.
In particular, by incorporating the titanium compound fine particles and the carbon black fine particles in the colored layer at a ratio satisfying the formula 0 ≤ ((a *) ² + (b *) ² ) ^0.5 ≤ 2, it is more natural. Color tones can be achieved, which is particularly preferable.

The titanium compound fine particles and the carbon black fine particles may be contained in either the coating layer or the pressure-sensitive adhesive layer, respectively. Then, both fine particles may be dispersed in the same layer or may be dispersed in different layers.
However, from the viewpoint of simplifying the manufacturing process, it is preferable that the titanium compound fine particles and the carbon black fine particles are both dispersed in the same layer of either the coating layer or the pressure-sensitive adhesive layer.

Further, it is more preferable that the titanium compound fine particles and the carbon black fine particles are contained in the coating layer rather than the pressure-sensitive adhesive layer. This is because when the adhesive layer contains titanium compound fine particles or carbon black fine particles, when the colored film according to the present invention is attached to a window or the like, the thickness of the adhesive is uniform in the plane due to the attaching pressure. This is because there is a possibility that color unevenness may occur due to the change in the amount of fine particles per area.

In the colored film having the pressure-sensitive adhesive layer, it is also preferable to laminate the release film on the surface of the pressure-sensitive adhesive layer from the practical viewpoint. Further, a film that is easily softened by heat such as a dryer may be used as the base film so that it can be easily attached to a curved surface such as a back window of an automobile.

Here, even in the case where both the titanium compound fine particles and the carbon black compound fine particles are contained in the pressure-sensitive adhesive layer, it is preferable to form the coating layer on at least one surface of the film substrate by using the coating resin. It is a composition.
This is because the formation of an appropriate coating layer on the surface of the film base material improves practical properties such as weather resistance and surface scratch resistance of the colored film base material.

As described above, the visible light transmittance of the colored film according to the present invention is determined by the total weight of the titanium compound fine particles and the carbon black fine particles per unit projected area on the colored film surface. The total weight of both fine particles per unit projected area is determined by appropriately controlling the weight ratio of both fine particles in the ink to the coating resin or the pressure-sensitive adhesive, or the thickness of the coating layer and / or the pressure-sensitive adhesive layer. , Easy to adjust.
The colored substrate according to the present invention has high weather resistance because both the titanium compound fine particles and the carbon black fine particles are inorganic compounds.

(3) Form of Colored Film and Colored Combined Substrate The colored film according to the present invention contains a thermoplastic resin and can be molded into a sheet-like, board-like or film-like form. ..
A known molding method can be applied.
By arranging one or more selected from the above-mentioned colored layer and colored film colored base material between a plurality of transparent base materials or sandwiching them between a plurality of transparent base materials, the colored combined base material according to the present invention is used. Will be.
Further, the transparent base material for forming the colored laminated base material is preferably glass.

The colored film and the colored combined substrate according to the present invention also have an L * a * b * tint calculated in a D65 light source and a 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004. In terms of values, the values of at least one of the transparent color coordinates or the reflected color coordinates, a * and b *, satisfy the equation 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 3.
In particular, by incorporating the titanium compound fine particles and the carbon black fine particles in the colored layer at a ratio satisfying the formula 0 ≤ ((a *) ² + (b *) ² ) ^0.5 ≤ 2, it is more natural. Color tones can be achieved, which is particularly preferable.

The optical characteristics and manufacturing conditions of the colored laminated base material according to the present invention can be considered in the same manner as those of the colored layer and the colored base material described above.

(4) Method for Producing Colored Layer and Colored Substrate The colored layer according to the present invention can be formed by using the coating ink according to the present invention or the pressure-sensitive adhesive layer forming liquid according to the present invention.
Further, the colored base material according to the present invention can be produced by using the transparent base material and the coating ink according to the present invention, or the transparent base material and the pressure-sensitive adhesive layer forming liquid according to the present invention.

Hereinafter, a method for manufacturing a colored layer and a colored base material will be specifically described using an example of a manufacturing process for a colored film as a colored base material according to the present invention, but the present invention is limited to this description. is not.
First, the coating ink according to the present invention is coated on the surface of the transparent film substrate, and then the solvent is evaporated. Then, by curing the coating resin by a predetermined method, a coating layer, which is a colored layer in which titanium compound fine particles and carbon black fine particles are dispersed in the coating resin, is formed on the surface of the transparent film base material, and the colored film according to the present invention is formed. Can be manufactured.

Further, by coating the surface of the transparent film substrate with the pressure-sensitive adhesive layer forming liquid according to the present invention and then evaporating the solvent, the pressure-sensitive adhesive layer, which is also a colored layer in which titanium compound fine particles and carbon black fine particles are dispersed in the medium, is formed. A colored film formed on the surface of a transparent substrate and according to the present invention can be produced.

When the coating layer or the pressure-sensitive adhesive layer is provided on the transparent film base material, the method for applying the coating ink according to the present invention may be any method as long as the ink can be uniformly applied to the surface of the transparent film base material. Not limited. For example, a bar coat method, a gravure coat method, a spray coat method, a dip coat method and the like can be mentioned.

Here, as a method for producing a colored film, the process of forming a coating layer is described by taking as an example a case where a coating layer is formed by using a bar coating method in a coating ink according to the present invention using an ultraviolet curable resin as a coating resin. explain.

When the coating ink according to the present invention is applied by the bar coating method, it is preferable to prepare the ink by appropriately adjusting the liquid concentration, additives and the like so as to have appropriate leveling property. Then, a coating film of the ink can be formed on the base film by using a wire bar having an appropriate bar number according to the desired thickness of the coating layer and the content of fine particles in the coating layer. Next, the solvent contained in the applied ink is removed by drying, and then the coating layer can be formed on the transparent film substrate by irradiating with ultraviolet rays and curing.
At this time, the drying conditions of the coating film of the coating ink vary depending on the components contained in the coating ink, the type of the solvent, and the usage ratio, but are, for example, about 20 seconds to 10 minutes at a temperature of 60 ° C to 140 ° C. By heating, the coating film of the coating ink can be dried.
Further, the method of irradiating ultraviolet rays is not particularly limited, and for example, a UV exposure machine such as an ultrahigh pressure mercury lamp can be preferably used.

In addition to the above operations, before and after the above-mentioned coating layer forming step, further appropriate steps are carried out to ensure the adhesion between the transparent film base material as a substrate and the coating layer, the smoothness of the coating film at the time of coating, and the solvent. It is also possible to control the dryness of the film. Examples of the steps arbitrarily performed before and after the coating layer forming step include a surface treatment step of the base material, a pre-baking (preheating of the base film) step, and a post-baking (post-heating of the base film) step. , Can be selected as appropriate. When the pre-baking step and / or the post-baking step is carried out, it is preferable that the heating temperature in the step is, for example, 80 ° C. to 200 ° C. and the heating time is 30 seconds to 240 seconds.
The thickness of the coating layer on the transparent film substrate is not particularly limited, but is preferably 10 μm or less, and more preferably 6 μm or less. This is because if the thickness of the coating layer is 10 μm or less, in addition to exhibiting sufficient pencil hardness and having scratch resistance, the transparent film base material is subjected to the volatilization of the solvent in the coating layer and the curing of the binder. This is because it is possible to suppress the occurrence of process abnormalities such as the occurrence of warpage.

(5) Method for Manufacturing Colored Film and Colored Combined Base Material The colored laminated base material according to the present invention is selected from the colored layer, the colored film having a sheet-like, board-like or film-like form, and the colored base material according to the present invention. It can be produced by arranging one or more kinds of the above-mentioned substances between a plurality of transparent substrates or sandwiching them between a plurality of transparent substrates.
Hereinafter, an example of a method for manufacturing a colored film and a colored laminated base material will be specifically described with reference to an example of a manufacturing process of the colored film and the colored laminated base material according to the present invention, but the present invention is limited to this description. It's not something.
The thermoplastic resin contained in the colored film used as the intermediate layer of the colored laminated base material is a polyvinyl acetal resin or an ethylene / vinyl acetate copolymer from the viewpoint of adhesion to a transparent base material, weather resistance, penetration resistance, etc. A polyvinyl butyral resin is more preferable, and a polyvinyl butyral resin is more preferable.

Further, when the thermoplastic resin constituting the colored film alone does not have sufficient flexibility and adhesion to the transparent substrate, for example, when the thermoplastic resin is a polyvinyl acetal resin, a plasticizer is further added. Is preferable.
As the plasticizer, a substance used as a plasticizer for the thermoplastic resin according to the present invention can be used. For example, as the plasticizer used for the heat ray shielding film made of polyvinyl acetal resin, a plasticizer which is a compound of a monovalent alcohol and an organic acid ester, a plasticizer which is an ester type such as a polyhydric alcohol organic acid ester compound, and the like. Examples thereof include phosphoric acid-based plasticizers such as organic phosphoric acid-based plasticizers. Both plasticizers are preferably liquid at room temperature. Of these, a plasticizer, which is an ester compound synthesized from a polyhydric alcohol and a fatty acid, is preferable.

After kneading the powdery or pelletized dispersion, the thermoplastic resin, and the plasticizer and other additives as desired, the kneaded product is subjected to a film by a known method such as an extrusion molding method or an injection molding method. A shaped colored film can be produced.
A known method can be used as a method for forming the film-shaped colored layer. For example, a calendar roll method, an extrusion method, a casting method, an inflation method, or the like can be used.
By interposing the film-shaped colored film thus produced as an intermediate layer between a plurality of transparent base materials made of a plate glass or a plastic material, the colored combined base material according to the present invention can be obtained. A known laminating method can be used in the method of obtaining a laminated base material by interposing a film-like dispersion between a plurality of transparent base materials.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
In the examples and comparative examples, the optical characteristics of the colored film were measured using a spectrophotometer U-4100 (manufactured by Hitachi, Ltd.).
Specifically, the procedure is as follows.
(1) The spectral transmittance (the light wavelength dependence of the transmittance) of the sample is measured with a spectrophotometer.
(2) The measured spectral transmittance is converted into an X ₁₀ Y ₁₀ Z ₁₀ tint value in a D65 light source and a 10 ° field of view based on JIS Z 8701.
(3) The converted X ₁₀ Y ₁₀ Z ₁₀ tint values are converted into L * a * b * tint values in a D65 light source and a 10 ° field of view based on JIS Z 8729, and a *, b * Get the value of.

As the film base material, a transparent PET film HPE-50 (manufactured by Teijin Limited, thickness 50 μm) (hereinafter, simply referred to as “PET film”) was used. When the optical characteristics of the PET film were measured, the visible light transmittance was 89.2% and the solar radiation transmittance was 89.2%. In the color coordinates, a * = 0.0, b * = 0.8, and the color difference ΔE from gray = ((a *) ² + (b *) ² ) ^0.5 is 0.8. rice field. This is shown in Table 1. In addition, the spectral transmittance of the PET film is shown in FIGS. 1 and 2 using fine solid lines.

(Example 1)
Acrylic polymer dispersant having a group containing 10% by mass of titanium nitride fine particles (average particle size 30 nm) and an amine as a functional group (amine value 48 mgKOH / g, acrylic dispersant having a decomposition temperature of 250 ° C.) (hereinafter, Dispersant a is abbreviated.) 10% by mass and 80% by mass of toluene were weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, and pulverized and dispersed for 13 hours to obtain a titanium nitride fine particle dispersion liquid (hereinafter, abbreviated as dispersion liquid A).

Weighed 10% by mass of carbon black fine particles (average particle size 15 nm), 10% by mass of dispersant a, and 80% by mass of toluene. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, and pulverized and dispersed for 7 hours to obtain a carbon black fine particle dispersion liquid (hereinafter, abbreviated as dispersion liquid B).

The dispersion liquid A and the dispersion liquid B were mixed so that the weight ratio of the titanium nitride fine particles and the carbon black fine particles contained in the coating ink described later was 100:30 to obtain a mixed ink. To 100 parts by weight of this mixed ink, 100 parts by weight of an ultraviolet curable resin (Aronix UV-3701 of Toagosei Co., Ltd., an acrylic ultraviolet curable resin having 100% active ingredient, hereinafter simply referred to as an ultraviolet curable resin), toluene. Was added in an amount of 800 parts by weight and then sufficiently mixed to obtain a coating ink according to Example 1 (hereinafter, abbreviated as coating ink A).

On the surface of the PET film, No. Using the wire bar of No. 6, the coating ink A was formed into a film by a bar coater. The film was dried at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet curable resin. As a result, a colored film according to Example 1 (hereinafter, abbreviated as colored film A) having a coating layer containing titanium nitride fine particles and carbon black fine particles was obtained.

The total weight of the coloring material per unit projected area contained in the coloring film was 0.16 g / m ² . Moreover, as a result of measuring the optical characteristics of the colored film, the visible light transmittance of the colored film A was 36.6%, and the solar radiation transmittance was 43.0%. In terms of color coordinates, a * =-1.1 and b * = 0.2, and the color difference ΔE = ((a *) ² + (b *) ² ) ^1/2 from gray was 1.1. .. This is shown in Table 1.

(Examples 2 to 6)
Similar to Example 1 except that the coating film thickness was changed by changing the bar number of the wire bar, the colored films according to Examples 2 to 6 (hereinafter, colored film B, colored film C, and colored film, respectively). D, colored film E, and colored film F) were obtained.
In Example 2, No. 10. In Example 3, No. 12. In Example 4, No. 18. In Example 5, No. 24, No. 6 in Example 6. Forty wire bars were used.
Then, the optical properties of the colored film B, the colored film C, the colored film D, the colored film E, and the colored film F are measured in the same manner as in Example 1, and are shown together with the total weight of the colored materials per unit projected area contained in the colored film. Shown in 1.

(Example 7)
The dispersion liquid A and the dispersion liquid B prepared in Example 1 were mixed so that the weight ratio of the titanium nitride fine particles and the carbon black fine particles contained in the ink was 100:50. By adding 100 parts by weight of the ultraviolet curable resin and 800 parts by weight of toluene to 100 parts by weight of the mixed ink and then mixing them sufficiently, the coating ink according to Example 7 (hereinafter, abbreviated as coating ink G). I got.).

On the surface of the PET film, No. Using the wire bar of No. 4, the coating ink G was formed into a film by a bar coater. The film was dried at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet curable resin. As a result, a colored film according to Example 7 (hereinafter, abbreviated as colored film G) having a coating layer containing titanium nitride fine particles and carbon black fine particles was obtained. Then, the optical properties of the colored film G were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.

(Example 8)
A colored film according to Example 8 (hereinafter abbreviated as colored film H) was obtained in the same manner as in Example 7 except that the coating film thickness was changed by changing the bar number of the wire bar. In Example 8, No. Eight wire bars were used.
Then, the optical properties of the colored film H were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.

(Example 9)
The dispersion liquid A and the dispersion liquid B prepared in Example 1 were mixed so that the weight ratio of the titanium nitride fine particles and the carbon black fine particles contained in the ink was 100: 70. 100 parts by weight of the ultraviolet curable resin and 800 parts by weight of toluene are added to 100 parts by weight of the mixed ink and then sufficiently mixed to obtain the coating ink according to Example 9 (hereinafter, abbreviated as coating ink I). I got.).

On the surface of the PET film, No. Using the wire bar of No. 3, the coating ink I was formed into a film by a bar coater. The film was dried at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet curable resin. As a result, a colored film according to Example 9 (hereinafter, abbreviated as colored film I) having a coating layer containing titanium nitride fine particles and carbon black fine particles was obtained. Then, the optical properties of the colored film I were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.

(Example 10)
The dispersion liquid A and the dispersion liquid B prepared in Example 1 were mixed so that the weight ratio of the titanium nitride fine particles and the carbon black fine particles contained in the ink was 100:25. 100 parts by weight of the ultraviolet curable resin and 800 parts by weight of toluene are added to 100 parts by weight of the mixed ink, and then the mixture is sufficiently mixed to form the coating ink according to Example 10 (hereinafter referred to as coating ink J). Abbreviated.) Was obtained.

On the surface of the PET film, No. Using the wire bar of No. 4, the coating ink J was formed into a film by a bar coater. The film was dried at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet curable resin. As a result, a colored film according to Example 10 (hereinafter, abbreviated as colored film J) having a coating layer containing titanium nitride fine particles and carbon black fine particles was obtained. Then, the optical properties of the colored film J were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.

(Examples 11 to 13)
The colored films according to Examples 11 to 13 (hereinafter, colored film K, colored film L, and colored film, respectively) are the same as in Example 10 except that the coating film thickness is changed by changing the bar number of the wire bar. (Abbreviated as M) was obtained. In Example 11, No. 10. In Example 12, No. 12. In Example 13, No. 16 wire bars were used.
Then, the optical properties of the colored film K, the colored film L, and the colored film M were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.

(Example 14)
The dispersion liquid A and the dispersion liquid B prepared in Example 1 were mixed so that the weight ratio of the titanium nitride fine particles and the carbon black fine particles contained in the ink was 100:15. By adding 100 parts by weight of the ultraviolet curable resin and 800 parts by weight of toluene to 100 parts by weight of the mixed ink and then mixing them sufficiently, the coating ink according to Example 14 (hereinafter, abbreviated as coating ink N). I got.).

On the surface of the PET film, No. Using the wire bar of No. 4, the coating ink N was formed into a film by a bar coater. The film was dried at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet curable resin. As a result, a colored film according to Example 14 (hereinafter, abbreviated as colored film N) having a coating layer containing titanium nitride fine particles and carbon black fine particles was obtained. Then, the optical properties of the colored film N were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.

(Example 15)
A colored film according to Example 15 (hereinafter abbreviated as colored film O) was obtained in the same manner as in Example 14 except that the coating film thickness was changed by changing the bar number of the wire bar. In Example 15, No. The wire bar of 6 was used.
Then, the optical properties of the colored film O were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.

(Example 16)
The dispersion liquid A and the dispersion liquid B prepared in Example 1 were mixed so that the weight ratio of the titanium nitride fine particles and the carbon black fine particles contained in the ink was 100:10. By adding 100 parts by weight of the ultraviolet curable resin and 800 parts by weight of toluene to 100 parts by weight of the mixed ink and then mixing them sufficiently, the coating ink according to Example 16 (hereinafter, abbreviated as coating ink P). I got.).

On the surface of the PET film, No. Using the wire bar of No. 4, the coating ink P was formed into a film by a bar coater. The film was dried at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet curable resin. As a result, a colored film according to Example 16 (hereinafter, abbreviated as colored film P) having a coating layer containing titanium nitride fine particles and carbon black fine particles was obtained. Then, the optical properties of the colored film P were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.

(Example 17)
Antimony-doped tin oxide (ATO) fine particles (average particle size 24 nm) were weighed in an amount of 10% by mass, dispersant a was weighed in an amount of 10% by mass, and toluene was weighed in an amount of 80% by mass. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, and pulverized and dispersed for 10 hours to obtain an ATO fine particle dispersion liquid (hereinafter, abbreviated as dispersion liquid C).

The dispersion liquid C and the dispersion liquid A and the dispersion liquid B prepared in Example 1 were mixed so that the weight ratio of the titanium nitride fine particles, the carbon black fine particles, and the ATO fine particles contained in the ink was 100: 40: 400. .. By adding 100 parts by weight of the ultraviolet curable resin and 50 parts by weight of toluene to 100 parts by weight of the mixed ink and then mixing them sufficiently, the coating ink according to Example 17 (hereinafter, abbreviated as coating ink Q). I got.).

On the surface of the PET film, No. Using 10 wire bars, the coating ink Q was formed into a film by a bar coater. The film was dried at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet curable resin. As a result, a colored film according to Example 17 (hereinafter, abbreviated as colored film Q) having a coating layer containing titanium nitride fine particles, carbon black fine particles, and ATO fine particles was obtained. Then, the optical properties of the colored film Q were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.

(Example 18)
Titanium nitride fine particles (average particle size 28 nm) were weighed by 10% by mass, dispersant a by 10% by mass, and toluene by 80% by mass. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, and pulverized and dispersed for 15 hours to obtain a titanium oxide fine particle dispersion (hereinafter abbreviated as dispersion D).

The dispersion liquid D and the dispersion liquid A prepared in Example 1 were mixed so that the weight ratio of the titanium nitride fine particles contained in the ink and the carbon black fine particles was 100:50. By adding 100 parts by weight of the ultraviolet curable resin and 800 parts by weight of toluene to 100 parts by weight of the mixed ink and then mixing them sufficiently, the coating ink according to Example 18 (hereinafter, abbreviated as coating ink R). I got.).

On the surface of the PET film, No. Using the wire bar of No. 6, the coating ink R was formed into a film by a bar coater. The film was dried at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet curable resin. As a result, a colored film according to Example 18 (hereinafter, abbreviated as colored film R) having a coating layer containing titanium oxide fine particles and carbon black fine particles was obtained. Then, the optical properties of the colored film R were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.

(Examples 19 to 22)
The colored films according to Examples 19 to 22 (hereinafter, colored film S, colored film T, and colored film, respectively) are the same as in Example 18 except that the coating film thickness is changed by changing the bar number of the wire bar. U, abbreviated as colored film V) was obtained. In Example 19, No. 9. In Example 20, No. 10. In Example 21, No. 14. In Example 22, No. Twenty-two wire bars were used.
Then, the optical properties of the colored film S, the colored film T, the colored film U, and the colored film V were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film. ..
In addition, the spectral transmittance of the colored film V obtained in Example 22 is shown in FIGS. 1 and 2 using thick solid lines.

(Example 23)
The dispersion liquid B prepared in Example 1 and the dispersion liquid D prepared in Example 18 were mixed so that the weight ratio of the titanium oxide fine particles contained in the ink and the carbon black fine particles was 100:80. By adding 100 parts by weight of the ultraviolet curable resin and 800 parts by weight of toluene to 100 parts by weight of the mixed ink and then mixing them sufficiently, the coating ink according to Example 23 (hereinafter, abbreviated as coating ink W). I got.).

On the surface of the PET film, No. Using the wire bar of No. 4, the coating ink W was formed into a film by a bar coater. The film was dried at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet curable resin. As a result, a colored film according to Example 23 (hereinafter, abbreviated as colored film W) having a coating layer containing titanium oxide fine particles and carbon black fine particles was obtained. Then, the optical characteristics of the colored film W were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.

(Example 24)
A colored film according to Example 24 (hereinafter abbreviated as colored film X) was obtained in the same manner as in Example 23 except that the coating film thickness was changed by changing the bar number of the wire bar. In Example 24, No. The wire bar of 5 was used.
Then, the optical properties of the colored film X were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.

(Example 25)
The dispersion liquid A and the dispersion liquid B prepared in Example 1 were mixed to obtain a mixed ink. At this time, the mixture was mixed so that the weight ratio of the titanium nitride fine particles and the carbon black fine particles contained in the mixed ink was 100:30.
Next, the dispersant a was added to the mixed ink. At this time, the ratio of the weight of the dispersant contained in the mixed ink to which the dispersant a is added to the total weight of the titanium nitride fine particles and the carbon fine particles is (weight of the dispersant) :( (titanium nitride fine particles). Dispersant a was added to the mixed ink so that (weight) + (weight of carbon fine particles)) = 900: 100.
The (weight of the dispersant) in the formula is the weight of the dispersant added when the dispersion A and the dispersion B were produced, and the dispersant added after mixing the dispersion A and the dispersion B. It represents the weight combined with the weight of.

The mixed ink to which the obtained dispersant a was added was loaded into a stirring vacuum dryer.
Then, it is dried under reduced pressure at room temperature by a stirring type vacuum dryer to remove toluene from the mixed ink to which the dispersant a is added, and the titanium nitride fine particles and carbon fine particles and the dispersant a which is a thermoplastic resin according to Example 25 are removed. A dispersion powder containing the above (hereinafter, abbreviated as dispersion powder Y) was obtained. The toluene content of the obtained dispersed powder Y was 2.9% by weight.

99.87 parts by weight of polycarbonate resin (manufactured by Teijin) powder and 0.13 parts by weight of dispersed powder Y are mixed, supplied to a twin-screw extruder set at 280 ° C., kneaded, and then extruded. It was formed into a sheet having a thickness of 1.0 mm. As a result, a sheet-shaped colored film (hereinafter, abbreviated as colored film Y) containing the polycarbonate resin which is the thermoplastic resin according to Example 25 was obtained.
The total weight of the coloring materials per unit projected area contained in the coloring film Y was 0.16 g / m ² . Further, as a result of measuring the optical characteristics of the colored film Y, the visible light transmittance was 35.9% and the solar radiation transmittance was 42.5%. In the color coordinates, a * =-1.0 and b * = 0.4, and the color difference ΔE = ((a *) ² + (b *) ² ) ^1/2 from gray was 1.1. ..

(Example 26)
Weighing 71.30 parts by weight of polyvinyl butyral resin powder, 28.52 parts by weight of triethylene glycol-di-2-ethylhexanoate as a plasticizer, and 0.18 parts by weight of the dispersion powder Y produced in Example 25. And mixed well to obtain a mixed composition. The obtained mixed composition was supplied to a twin-screw extruder set at 200 ° C. for kneading, and then extruded from a T-die by a calender roll method to form a 0.76 mm thick film. As a result, as the thermoplastic resin according to Example 25, a film-shaped colored film containing a polyvinyl butyral resin (hereinafter, abbreviated as colored film Z) was produced.

The prepared colored film Z is temporarily sandwiched between two transparent float glasses (thickness of 3 mm), the temporary sandwiched object is heated to 130 ° C., and a pressing process is performed for 5 minutes under vacuum to obtain a colored laminated substrate (a colored laminated substrate (3 mm thick). Hereinafter, it is abbreviated as a colored laminated base material Z).
The total weight of the colored materials per unit projected area contained in the obtained colored combined substrate Z was 0.16 g / m ² . Further, as a result of measuring the optical characteristics of the colored laminated base material Z, the visible light transmittance was 35.0% and the solar radiation transmittance was 42.6%. In the color coordinates, a * =-1.1, b * = 0.6, and the color difference ΔE = ((a *) ² + (b *) ² ) ^1/2 from gray was 1.3. ..

(Comparative Example 1)
Comparative Example 1 was obtained by adding 100 parts by weight of the ultraviolet curable resin and 800 parts by weight of toluene to 100 parts by weight of the dispersion liquid A, which is the titanium nitride dispersion liquid produced in Example 1, and then mixing them sufficiently. The coating ink (hereinafter, abbreviated as coating ink α) was obtained.

On the surface of the PET film, No. Using 24 wire bars, the coating ink α was formed into a film by a bar coater. The film was dried at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet curable resin. As a result, a colored film according to Comparative Example 1 (hereinafter, abbreviated as colored film α) having a coating layer containing titanium nitride fine particles and not carbon black fine particles was obtained. Then, the optical characteristics of the colored film α were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.
In addition, the spectral transmittance of the colored film α obtained in Comparative Example 1 is shown in FIGS. 1 and 2 using the alternate long and short dash line.

(Comparative Example 2)
Comparative Example 2 was obtained by adding 100 parts by weight of the ultraviolet curable resin and 800 parts by weight of toluene to 100 parts by weight of the dispersion liquid B, which is the carbon black dispersion liquid produced in Example 1, and then mixing them sufficiently. The coating ink (hereinafter, abbreviated as coating ink β) was obtained.

On the surface of the PET film, No. Using 10 wire bars, the coating ink β was formed into a film by a bar coater. The film was dried at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet curable resin. As a result, a colored film according to Comparative Example 2 (hereinafter, abbreviated as colored film β) having a coating layer containing carbon black fine particles and not containing titanium nitride fine particles was obtained. Then, the optical properties of the colored film β were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.
Moreover, the spectral transmittance of the colored film β obtained in Comparative Example 2 is shown in FIGS. 1 and 2 using a long broken line.

(Comparative Example 3)
10% by mass of Heliogen Blue D 6700 T (manufactured by BASF), which is a copper phthalocyanine blue pigment (CI Pigment Blue 15: 6), 10% by mass of dispersant a, and 80% by mass of toluene were weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, pulverized and dispersed for 5 hours to obtain a copper phthalocyanine blue pigment dispersion (hereinafter abbreviated as dispersion E).

By adding 100 parts by weight of the ultraviolet curable resin and 800 parts by weight of toluene to 100 parts by weight of the dispersion liquid E and then mixing them sufficiently, the coating ink according to Comparative Example 3 (hereinafter referred to as the coating ink γ) is sufficiently mixed. Abbreviated.) Was obtained.
On the surface of the PET film, No. Using 10 wire bars, the coating ink γ was formed into a film by a bar coater. The film was dried at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet curable resin. As a result, a colored film according to Comparative Example 3 (hereinafter, abbreviated as colored film γ) containing a copper phthalocyanine pigment and having a coating layer containing neither titanium nitride fine particles nor carbon black fine particles was obtained. rice field. Then, the optical characteristics of the colored film γ were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.
Moreover, the spectral transmittance of the colored film γ obtained in Comparative Example 3 is shown in FIGS. 1 and 2 using a short broken line.

(Comparative Example 4)
10% by mass of iron oxide (Fe ₂ O ₃ ) fine particles (average particle size 30 nm), 10% by mass of dispersant a, and 80% by mass of toluene were weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads, and pulverized and dispersed for 12 hours to obtain an iron oxide fine particle dispersion liquid (hereinafter, abbreviated as dispersion liquid F).

The dispersion liquid F and the dispersion liquid A prepared in Example 1 were mixed so that the weight ratio of the titanium nitride fine particles and the iron oxide fine particles contained in the ink was 100:45. By adding 100 parts by weight of the ultraviolet curable resin and 800 parts by weight of toluene to 100 parts by weight of the mixed ink and then mixing them sufficiently, the coating ink according to Comparative Example 4 (hereinafter, abbreviated as coating ink δ). I got.).

On the surface of the PET film, No. Using 20 wire bars, the coating ink δ was formed into a film by a bar coater. The film was dried at 70 ° C. for 1 minute to evaporate the solvent, and then irradiated with ultraviolet rays using a high-pressure mercury lamp to cure the ultraviolet curable resin. As a result, a colored film according to Comparative Example 4 (hereinafter, abbreviated as colored film δ) having a coating layer containing titanium nitride fine particles and not carbon black fine particles was obtained. Then, the optical properties of the colored film δ were measured in the same manner as in Example 1, and are shown in Table 1 together with the total weight of the colored materials per unit projected area contained in the colored film.
Further, the spectral transmittance of the colored film δ obtained in Comparative Example 4 is shown in FIGS. 1 and 2 using a broken line.

(Evaluation of Examples 1 to 26 and Comparative Examples 1 to 4)
The colored films according to Examples 1 to 16 and Examples 18 to 24 contain titanium compound fine particles and carbon black fine particles in an appropriate ratio in the coating layer. Therefore, while the colored film uses only inorganic fine particles having high weather resistance, ΔE = ((a *) ² + (b *) ² ) ^1/2 is 0 or more 3 even in a region where the visible light transmittance is low. It had the following natural tones.
The colored films according to Examples 25 and 26, and the colored laminated base material according to Example 26 using the same, also have titanium compound fine particles and carbon black fine particles in appropriate proportions in the same manner as in Examples 1 to 24 described above. Since it was contained, ΔE = ((a *) ² + (b *) ² ) ^1/2 had a natural color tone of 0 or more and 3 or less even in the region where the visible light transmittance was low.

In particular, the spectral transmittance of the colored film according to Example 22 shown in FIGS. 1 and 2 exhibits flat transmittance in the visible light region having a wavelength of 380 to 780 nm, and particularly in the region having a wavelength of 450 to 750 nm. The transmittance was almost constant.

Further, in the colored films according to Examples 1 to 16 and 18 to 24, the colored film according to Example 25, and the colored combined substrate according to Example 26, all of the titanium nitride fine particles and the carbon black fine particles are used. Has absorption at wavelengths in the near-infrared region, so a low value of solar transmittance was obtained.
In the colored film according to Example 17, in addition to the above configuration, by further having infrared-absorbing fine particles in the coating layer, ΔE = ((a *) ² + (b *) ² ) ^1/2 is 0 or more and 3 A lower solar transmittance was obtained as compared with the colored films according to the other examples, which had the same level of visible light transmittance and did not contain infrared-absorbing fine particles while maintaining the following natural color tones. ..

Since the colored film according to Comparative Examples 1 and 2 contained only one of the titanium nitride fine particles and the carbon black dispersion liquid, the color tone was significantly different from the natural color tone.
In the colored film according to Comparative Example 3, copper phthalocyanine blue, which is a blue organic pigment, largely cuts visible light, but absorption on the short wavelength side of visible light is not sufficient as compared with the long wavelength side of visible light. It was very different from the natural color. Further, since copper phthalocyanine blue has almost no absorption in the near-infrared region on the longer wavelength side than the wavelength of 780 nm, the suppression of the solar transmittance is not sufficient. Therefore, as compared with the colored film according to the example having the same visible light transmittance, the film has a very high solar transmittance and is significantly inferior in heat shielding characteristics.
The colored film according to Comparative Example 4 is a combination of titanium nitride fine particles having a relatively strong absorption in the long visible light wavelength region and iron oxide fine particles having a relatively strong absorption in the short wavelength region of visible light as in carbon black. This is an example. However, due to the absorption characteristics of iron oxide, even when combined with titanium nitride, it was not possible to have a flat transmittance over the entire range of visible light, which was different from the natural color tone. This was the same even if the blending ratio of titanium nitride and iron oxide was changed.

From the absorption data in the visible light long wavelength region of the colored film according to Comparative Example 4, it is shown again that the composition of the colored film and the colored layer according to the present invention is an epoch-making one that solves the above-mentioned problems. rice field.

Claims (18)

Titanium compound fine particles and carbon black fine particles are dispersed in the medium,
The titanium compound fine particles are one or more selected from titanium nitride fine particles, titanium oxide fine particles, and weakly reduced titanium oxide fine particles.
The titanium nitride fine particles have a molar ratio of Ti to N in the range of 1: 1 to ± 20%.
The titanium oxide fine particles have a molar ratio of Ti to N + O in the range of 1: 1 to ± 20%.
The weakly reduced titanium oxide fine particles are in the range of 0.02 ≦ x ≦ 0.8 in the composition formula TiO _2-x .
The average dispersed particle size of the titanium compound fine particles is 40 nm or less and 1 nm or more.
The average dispersed particle size of the carbon black fine particles is 30 nm or less and 1 nm or more.
The weight ratio of the titanium compound fine particles to the carbon black fine particles is in the range of [titanium compound fine particles] / [carbon black fine particles] = 100: 10 to 100: 100.
When a colored layer is formed on a substrate and the total weight of the titanium compound fine particles and the carbon black compound fine particles contained per unit projected area is 0.05 g / m ² or more and 1.50 g / m ² or less. ,
The visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0.5% or more and 40% or less.
In the L * a * b * tint values calculated in the D65 light source and 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004, the values of the transmitted color coordinates a * and b * are expressed in the formula 0. ≤ ((a *) ² + (b *) ² ) A dispersion characterized by satisfying ^0.5 ≤ 2. The dispersion according to claim 1, further comprising infrared-absorbing fine particles. 2. The invention is characterized in that the infrared absorbing fine particles are one or more selected from tungsten oxide fine particles, composite tungsten oxide fine particles, boride fine particles, antimony-added tin oxide fine particles, and tin-added indium oxide fine particles. Dispersion described in. The dispersion according to any one of claims 1 to 3, wherein the medium is an inorganic binder and / or an organic binder. The dispersion according to claim 4, wherein the organic binder is one or more selected from an ultraviolet curable resin, a thermosetting resin, an electron beam curable resin, a room temperature curable resin, and a thermoplastic resin. Titanium compound fine particles and carbon black fine particles are dispersed in the medium,
The titanium compound fine particles are one or more selected from titanium nitride fine particles, titanium oxide fine particles, and weakly reduced titanium oxide fine particles.
The titanium nitride fine particles have a molar ratio of Ti to N in the range of 1: 1 to ± 20%.
The titanium oxide fine particles have a molar ratio of Ti to N + O in the range of 1: 1 to ± 20%.
The weakly reduced titanium oxide fine particles are in the range of 0.02 ≦ x ≦ 0.8 in the composition formula TiO _2-x .
The average dispersed particle size of the titanium compound fine particles is 40 nm or less and 1 nm or more.
The average dispersed particle size of the carbon black fine particles is 30 nm or less and 1 nm or more.
A dispersion in which the weight ratio of the titanium compound fine particles to the carbon black fine particles is in the range of [titanium compound fine particles] / [carbon black fine particles] = 100: 10 to 100: 100 is formed on the substrate. It is a colored layer that is
The total weight of the titanium compound fine particles and the carbon black compound fine particles contained per unit projected area is 0.05 g / m ² or more and 1.50 g / m ² or less.
The visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0.5% or more and 40% or less.
In the L * a * b * tint values calculated in the D65 light source and 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004, the values of the transmitted color coordinates a * and b * are expressed in the formula 0. ≤ ((a *) ² + (b *) ² ) A colored layer characterized by satisfying ^0.5 ≤ 2. The colored layer according to claim 6, wherein the base material is resin or glass. Titanium compound fine particles and carbon black fine particles are dispersed in the medium,
The titanium compound fine particles are one or more selected from titanium nitride fine particles, titanium oxide fine particles, and weakly reduced titanium oxide fine particles.
The titanium nitride fine particles have a molar ratio of Ti to N in the range of 1: 1 to ± 20%.
The titanium oxide fine particles have a molar ratio of Ti to N + O in the range of 1: 1 to ± 20%.
The weakly reduced titanium oxide fine particles are in the range of 0.02 ≦ x ≦ 0.8 in the composition formula TiO _2-x .
The average dispersed particle size of the titanium compound fine particles is 40 nm or less and 1 nm or more.
The average dispersed particle size of the carbon black fine particles is 30 nm or less and 1 nm or more.
A molded body of a dispersion in which the weight ratio of the titanium compound fine particles to the carbon black fine particles is in the range of [titanium compound fine particles] / [carbon black fine particles] = 100: 10 to 100: 100.
The molded body has a film-like, sheet-like, or board-like shape.
The total weight of the titanium compound fine particles and the carbon black compound fine particles contained per unit projected area is 0.05 g / m ² or more and 1.50 g / m ² or less.
The visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0.5% or more and 40% or less.
In the L * a * b * tint values calculated in the D65 light source and 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004, the values of the transmitted color coordinates a * and b * are expressed in the formula 0. ≤ ((a *) ² + (b *) ² ) A colored film characterized by satisfying ^0.5 ≤ 2. The colored film according to claim 8, wherein the colored film contains a thermoplastic resin. A colored substrate, wherein at least one selected from the colored layer according to claim 6 or 7 and the colored film according to claim 8 or 9 is provided on a transparent substrate. .. The visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0.5% or more and 40% or less.
In the L * a * b * tint values calculated in the D65 light source and 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004, the values of the transmitted color coordinates a * and b * are expressed in the formula 0. ≤ ((a *) ² + (b *) ² ) The colored substrate according to claim 10, wherein ^0.5 ≤ 2 is satisfied. The colored substrate according to claim 10 or 11, wherein the transparent substrate is a resin or glass. A plurality of one or more selected from the colored layer according to claim 6 or 7, the colored film according to claim 8 or 9, and the colored substrate according to any one of claims 10 to 12. A colored combined substrate characterized by being provided between the transparent substrates of the above. The visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0.5% or more and 40% or less.
In the L * a * b * tint values calculated in the D65 light source and 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004, the values of the transmitted color coordinates a * and b * are expressed in the formula 0. ≤ ((a *) ² + (b *) ² ) The colored combined substrate according to claim 13, wherein ^0.5 ≤ 2 is satisfied. The colored combined substrate according to claim 13 or 14, wherein the transparent substrate is a resin or glass. An ink containing titanium compound fine particles, carbon black fine particles, and one or more selected from an organic solvent or water.
The titanium compound fine particles are one or more selected from titanium nitride fine particles, titanium oxide fine particles, and weakly reduced titanium oxide fine particles.
The titanium nitride fine particles have a molar ratio of Ti to N in the range of 1: 1 to ± 20%.
The titanium oxide fine particles have a molar ratio of Ti to N + O in the range of 1: 1 to ± 20%.
The weakly reduced titanium oxide fine particles are in the range of 0.02 ≦ x ≦ 0.8 in the composition formula TiO _2-x .
The average dispersed particle size of the titanium compound fine particles is 40 nm or less and 1 nm or more.
The average dispersed particle size of the carbon black fine particles is 30 nm or less and 1 nm or more.
The weight ratio of the titanium compound fine particles contained in the ink to the carbon black fine particles is in the range of [titanium compound fine particles] / [carbon black fine particles] = 100: 10 to 100: 100.
Using the ink, a colored layer on a transparent substrate in which the total weight of the titanium compound fine particles and the carbon black compound fine particles contained per unit projected area is 0.05 g / m ² or more and 1.50 g / m ² or less. JIS Z 8701: 1999 and JIS when the visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0.5% or more and 40% or less in the optical characteristics of the colored substrate having formed the above. In the L * a * b * tint values calculated in the D65 light source and 10-degree field of view based on Z 8729: 2004, the values of the transmitted color coordinates a * and b * are expressed by the formula 0 ≦ ((a *) ² ). + (B *) ² ) An ink characterized by satisfying ^0.5 ≤ 2. The ink according to claim 16, further comprising infrared-absorbing fine particles. 17. The infrared absorbing fine particles are one or more selected from tungsten oxide fine particles, composite tungsten oxide fine particles, boride fine particles, antimony-added tin oxide fine particles, and tin-added indium oxide fine particles. Ink described in.

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