JP2016210984A - Dispersion, colored layer, colored film, colored substrate, colored laminate substrate and ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored substrate capable of achieving natural color tone by a combination of few kinds of coloring materials, high in weather resistance and capable of industrially being achieved, a colored laminate substrate, a dispersion used for manufacturing them and an ink.SOLUTION: There are provided a dispersion and an ink where titanium compound fine particles and carbon black fine particles are dispersed in a medium and the weight ratio of the titanium compound fine particles and the carbon black fine particles is in a range of [titanium compound fine particles]/[carbon black fine particles]=100:10 to 100:100.SELECTED DRAWING: Figure 1

Description

  The present invention is, for example, a dispersion, a colored layer, a colored film, a colored base material, or a colored match that does not have a color tone such as reddish, bluish, greenish, and yellowish, which are used in automobiles and other transportation equipment and building material windows The present invention relates to a substrate and ink.

  Most of the windows of transportation equipment and building materials such as automobiles are transparent and have high transmittance of ultraviolet rays, visible rays and infrared rays. In order to prevent vehicle passengers from being dazzled by sunlight, to improve comfort in the vehicle and the interior of the vehicle, to improve cooling efficiency and vehicle fuel consumption, and to protect privacy by shielding human eyes, the windows are not completely blocked. There is a demand in the market for a colored base material, an affixed film, and the like that moderately reduce the transmittance.

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

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

Japanese Patent Laid-Open No. 9-12018

Here, for example, an operator of the transport device needs to recognize the various signals and traffic conditions accurately from the window. For this reason, the coloring base material and colored film which do not have color tone, such as redness, blueness, greenness, and yellowness, are calculated | required for the coloring base material and coloring film provided in the window of a transport apparatus.
In recent years, there has been a demand for colored substrates and colored films that do not have a color tone such as reddish, bluish, greenish, and yellowish in fields such as the transportation equipment field, as well as in the fields of architecture, industrial fields, optical elements, and sunglasses. ing.
In the present invention, the colored base material having no color tone such as reddish, bluish, greenish, and yellowish is the same as the “colored substrate having a natural color tone”, as well as reddish, bluedish. A colored film having no color tone such as green and yellow may be referred to as a “film having a natural color tone”.

However, as a result of studies by the present inventors, the following problems have been found.
That is, the above-described colored base material and colored film according to the prior art cannot realize a natural color tone at a high level in a wavelength region having a low visible light transmittance. Moreover, it is that the weather resistance of the said colored base material and a colored film is low.

  Here, the present inventors have conducted research, and a colored substrate or colored film having a natural color tone “absorbs”, “shields”, or “transmits” light of a specific wavelength in the wavelength region of visible light. I realized that there was nothing. In other words, the colored substrate or colored film uniformly “absorbs”, “shields”, or “transmits” light in the visible light wavelength region, so that red, blue, green in human vision. We thought that it would be a colored substrate or colored layer that would not perceive the color tone such as taste and yellowness.

  For example, a colored film in which a colored base material, adhesive or hard coat is colored with a black organic dye material such as aniline black according to the prior art, the black organic dye material emits light evenly in the entire visible light region. Therefore, it was not a colored base material having a natural color tone. Furthermore, since the weather resistance of the black organic dye material is not sufficient, the optical characteristics are deteriorated and the light-shielding performance is deteriorated even when used for a very short time.

In addition, for example, a colored base material or colored film obtained by coloring a transparent base material such as a film or board, an adhesive layer, or a hard coat with carbon black, the absorption of the carbon black is short wavelength side and long wavelength side of visible light. Therefore, it did not have a natural color tone.
In addition, for example, a colored substrate or colored film colored with a highly weather-resistant colored pigment, such as a phthalocyanine blue pigment, because the phthalocyanine blue pigment absorbs only light in a partial wavelength region of visible light, After all, it did not have a natural color.

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

  The present invention has been made under the above-mentioned circumstances, and the problem to be solved is that a natural color tone can be realized with a combination of a small number of coloring materials, weather resistance is high, and it can be industrially realized. A colored layer, a colored film, a colored substrate, a colored matching substrate, a dispersion used in the production thereof, and an ink.

  The present inventors conducted research in order to solve the above 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. A dispersion, a colored layer, a colored film, a colored base material, and a colored matching base material prepared by applying the ink are only a combination of two kinds of coloring materials, and the industrial implementation is easy. First, it was found that a specific natural color tone can be realized in the transmitted color and the reflected color in a region where the visible light transmittance is low.

Specifically, a colored layer, a colored film, a colored base material, and a colored matching base material having the above-described configuration are calculated with a D65 light source and a 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004. In the L * a * b * color value, the value of a * and b * of at least one of the transmission color coordinates or the reflection color coordinates is expressed by 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.

In addition, the structure of the coloring base material which concerns on this invention, and a coloring matching base material is as follows.
The colored substrate has a configuration in which at least one surface of the substrate has a coating layer or a pressure-sensitive adhesive layer, and at least one layer selected from the coating layer or the pressure-sensitive adhesive layer is a colored layer.
Further, the color matching substrate has a plurality of transparent substrates and at least one selected from a colored layer, a colored film, and a colored substrate, and is selected from a colored layer, a colored film, and a colored substrate. One or more types have the structure arrange | positioned between the said several transparent base materials.

  The inventors of the present invention provide a dispersion in which titanium compound fine particles and carbon black fine particles are dispersed in a medium, or an ink containing titanium compound fine particles, carbon black fine particles, and an organic solvent or water. It has also been found that it is suitable as a dispersion and an ink for producing a dispersion, a colored substrate, and a colored matching substrate.

Furthermore, when the present inventors use at least one of titanium nitride fine particles, titanium oxynitride fine particles, and weakly reduced titanium oxide fine particles as the titanium compound described above, the dispersion having the above-described configuration, a colored substrate, and coloring It has been found that a natural color tone can be realized particularly in the laminated base material and the ink.
The inventors have conceived 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 found that the colored substrate having the above-described configuration has a low solar transmittance as compared with a colored substrate such as a colored film produced by the prior art, and can be used as a heat shielding substrate. The present invention was completed by finding out that it has high performance.

That is, the first invention for solving the above-described problem is
Titanium compound fine particles and carbon black fine particles are dispersed in the medium,
The dispersion is characterized in that 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 second invention is
The average dispersion particle diameter of the titanium compound fine particles is 1 nm or more and 100 nm or less. The dispersion according to the first invention.
The third invention is
The dispersion according to the first or second invention, wherein the carbon black fine particles have an average dispersed particle diameter of 1 nm to 100 nm.
The fourth invention is:
The dispersion according to any one of the first to third inventions, wherein the titanium compound fine particles are at least one selected from titanium nitride fine particles, titanium oxynitride fine particles, and weakly reduced titanium oxide fine particles. is there.
The fifth invention is:
The dispersion according to any one of the first to fourth inventions, further comprising infrared absorbing fine particles.
The sixth invention is:
The infrared absorbing fine particles are at least one 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, The dispersion according to the invention.
The seventh invention
The dispersion according to any one of the first to sixth inventions, wherein the medium is an inorganic binder and / or an organic binder.
The eighth invention
The dispersion according to the seventh invention, wherein the organic binder is at least one selected from an ultraviolet curable resin, a thermosetting resin, an electron beam curable resin, a room temperature curable resin, and a thermoplastic resin. is there.
The ninth invention
A colored layer, wherein the dispersion according to any one of the first to eighth inventions is formed on a substrate.
The tenth invention is
The visible light transmittance calculated by the method defined in JIS R 3106: 1998 is 0% or more and 60% or less,
In the L * a * b * color value calculated in JIS Z 8701: 1999 and JIS Z 8729: 2004 with a D65 light source and a 10-degree field of view, at least one of the transmitted color coordinates and the reflected color coordinates a * and b The colored layer according to the ninth aspect, wherein the value of * satisfies the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 3.
The eleventh invention is
The colored layer according to the tenth invention, wherein the values of the color coordinates a * and b * satisfy the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2. It is.
The twelfth invention
Wherein the total weight of the titanium compound particles and carbon black compound fine particles contained in the per unit projected area is 0.05 g / m ² or more 1.50 g / m ² or less, from the ninth to the eleventh aspect of The colored layer according to any one of the above.
The thirteenth invention
The colored layer according to any one of the ninth to twelfth inventions, wherein the base material is resin or glass.
The fourteenth invention is
A molded body of the dispersion according to any one of the first to eighth inventions,
The colored film is characterized in that the molded body has any one of a film shape, a sheet shape, and a board shape.
The fifteenth invention
The visible light transmittance calculated by the method defined in JIS R 3106: 1998 is 0% or more and 60% or less,
In the L * a * b * color value calculated in JIS Z 8701: 1999 and JIS Z 8729: 2004 with a D65 light source and a 10-degree field of view, at least one of the transmitted color coordinates and the reflected color coordinates a * and b The colored film according to the fourteenth aspect, wherein the value of * satisfies the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 3.
The sixteenth invention is
The colored film according to the fifteenth aspect, wherein the values of the color coordinates a * and b * satisfy the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2. It is.
The seventeenth invention
Wherein the total weight of the titanium compound particles and carbon black compound fine particles contained in the per unit projected area is 0.05 g / m ² or more 1.50 g / m ² or less, from the fourteenth invention of a 16 The colored film according to any one of the above.
The eighteenth invention
The colored film according to any one of the fourteenth to seventeenth inventions, wherein the colored film contains a thermoplastic resin.
The nineteenth invention
A dispersion according to any one of the first to eighth inventions, wherein the dispersion is a powder.
The twentieth invention is
A dispersion according to any one of the first to eighth aspects, wherein the dispersion is in the form of pellets.
The twenty-first invention
Any one or more selected from the colored layer according to any one of the ninth to thirteenth inventions and the colored film according to any one of the fourteenth to eighteenth aspects is provided on the transparent substrate. It is the coloring base material characterized by the above-mentioned.
The twenty-second invention relates to
The visible light transmittance calculated by the method defined in JIS R 3106: 1998 is 0% or more and 60% or less,
In the L * a * b * color value calculated in JIS Z 8701: 1999 and JIS Z 8729: 2004 with a D65 light source and a 10-degree field of view, at least one of the transmitted color coordinates and the reflected color coordinates a * and b The colored substrate according to the twenty-first aspect, wherein the value of * satisfies the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 3.
The twenty-third invention
The coloring group according to the twenty-second invention, wherein the values of the color coordinates a * and b * satisfy the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2. It is a material.
The twenty-fourth invention is
The colored substrate according to any one of the twenty-first to twenty-third aspects, wherein the transparent substrate is a resin or glass.
The twenty-fifth invention
From the colored layer according to any one of the ninth to thirteenth inventions, the colored film according to any one of the fourteenth to eighteenth inventions, the colored substrate according to any one of the twenty-first to twenty-fourth inventions, Any one or more selected is a colored matching base material provided between a plurality of transparent base materials.
The twenty-sixth invention
The visible light transmittance calculated by the method defined in JIS R 3106: 1998 is 0% or more and 60% or less,
In the L * a * b * color value calculated in JIS Z 8701: 1999 and JIS Z 8729: 2004 with a D65 light source and a 10-degree field of view, at least one of the transmitted color coordinates and the reflected color coordinates a * and b The colored matching substrate according to the 25th aspect, wherein the value of * satisfies the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 3.
The twenty-seventh invention
The color matching according to the twenty-sixth invention, wherein the values of the color coordinates a * and b * satisfy the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2. It is a substrate.
The twenty-eighth invention is
The colored matching substrate according to any one of the 25th to 27th inventions, wherein the transparent substrate is resin or glass.
The twenty-ninth invention
An ink containing titanium compound fine particles, carbon black fine particles, and one or more selected from an organic solvent or water,
Using said ink, onto a transparent substrate, the total weight of the titanium compound particles and carbon black compound fine particles contained in the per unit projected area is 0.05 g / m ² or more 1.50 g / m ² or less colored layer JIS Z 8701: 1999 and JIS Z 8729 when the visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0% or more and 60% or less in the optical characteristics of the colored base material formed with JIS Z 3729: In the L * a * b * color value calculated with a D65 light source and a 10-degree field of view based on 2004, the value of a * and b * of at least one of the transmission color coordinates or the reflection color coordinates is expressed by the expression 0 ≦ (( a *) ² + (b *) ² ) An ink that satisfies ^0.5 ≦ 3.
The thirtieth invention is
The ink according to the 29th aspect, wherein the values of the color coordinates a * and b * satisfy the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2. .
The thirty-first invention
The weight ratio between the titanium compound fine particles and the carbon black fine particles contained in the ink is in the range of [titanium compound fine particles] / [carbon black fine particles] = 100: 10 to 100: 100. The ink according to 29th or 30th invention.
The thirty-second invention
32. The ink according to any one of claims 29 to 31, wherein an average dispersed particle size of the titanium compound fine particles is 1 nm or more and 100 nm or less.
The thirty-third invention
The ink according to any one of the twenty-ninth to thirty-second inventions, wherein the carbon black fine particles have an average dispersed particle diameter of 1 nm to 50 nm.
The thirty-fourth invention is
34. The ink according to any one of claims 29 to 33, wherein the titanium compound fine particles are at least one selected from titanium nitride fine particles, titanium oxynitride fine particles, and weakly reduced titanium oxide fine particles. .
The thirty-fifth invention
The ink according to any one of the twenty-ninth to thirty-fourth inventions, further comprising infrared absorbing fine particles.
The thirty-sixth invention is
35. The thirty-fifth aspect, wherein 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. The ink according to the invention.

  The colored layer, colored film, colored base material, and colored matching base material according to the present invention manufactured using the dispersion or ink according to the present invention has a natural color tone despite being a combination of two kinds of colored materials. High weather resistance and easy to implement industrially.

It is the permeation | transmission curve of the colored film and base material film which were measured in Example 21, Comparative Examples 1-4, and Reference Example 1. FIG. It is the transmission curve which expanded the wavelength region vicinity of visible light and the area | region of the low transmittance | permeability from the colored film and base film transmission curve measured in Example 21, Comparative Examples 1-4, and Reference Example 1. FIG.

Hereinafter, embodiments of the present invention will be described in detail.
The dispersion according to the present invention is a concept indicating 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 a silicone resin, and the organic binder is at least one selected from an ultraviolet curable resin, a thermosetting resin, an electron beam curable resin, a room temperature curable resin, and a thermoplastic resin. preferable.
Preferably, it is a concept indicating a state in which at least titanium compound fine particles and carbon black fine particles are dispersed in a solid medium.

In addition, when the dispersion is formed as a coating layer, a pressure-sensitive adhesive layer, or the like 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”. There is a case.
In addition, when the dispersion is contained in a resin and the resin is molded into a film shape, a sheet shape, a board shape, or the like, the molded body may be described as a “colored film”.
On the other hand, when the dispersion is in powder form, the powder may be referred to as “dispersion powder”.
Furthermore, when the dispersion is in the form of pellets, the pellets may be referred to as “master batches”.

Next, the ink according to the present invention is:
(A) a dispersion 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 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,
This is a concept including the dispersion liquid and the coating liquid.
In order to distinguish the above concepts, (a) is “dispersion liquid” or “fine particle dispersion liquid”, (b) is “coating ink”, and (c) is “adhesive layer forming liquid”. May be described.

  The colored layer according to the present invention described above contains titanium compound fine particles and carbon black fine particles such as a coating layer such as a hard coat manufactured using the ink described above and an adhesive layer manufactured using the ink described above. It is also a concept that includes a colored layer.

  Next, the colored base material according to the present invention is in a form having at least one type of colored layer selected from the above-described coating layer and pressure-sensitive adhesive layer and / or the above-described colored film on at least one surface of the transparent base material. . Further, at least one layer of the coating layer or the pressure-sensitive adhesive layer is a concept including a titanium compound fine particle, and at least one layer of the coating layer or the pressure-sensitive adhesive layer includes a carbon black fine particle.

  And the coloring matching base material which concerns on this invention is the concept which shows the matching base material in which 1 or more types selected from the colored layer mentioned above, a coloring film | membrane, and a coloring base material exist among several transparent base materials. .

  Hereinafter, [1] ink, dispersion, colored matching base material and components constituting the colored base material, [2] forms of ink, dispersion powder and masterbatch and production method thereof, [3] colored layer, The colored base material, the colored film, the colored matching base material, and the manufacturing method thereof will be described in detail.

[1] Ingredients constituting ink, dispersion, colored layer, colored film, colored substrate and colored matching substrate As components constituting ink, dispersion, colored layer, colored film, colored substrate and colored matching substrate (1) Titanium compound fine particles, (2) Carbon black fine particles, (3) Solvent, (4) Dispersant, (5) Infrared absorbing compound, (6) Coating resin, (7) Adhesive, (8) Other The additive will be described in detail in the order of (9) transparent substrate and (10) thermoplastic resin.

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

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

  Here, the titanium oxynitride fine particles are fine particles corresponding to the above-described titanium nitride fine particles obtained by substituting a part of N with O. Also in the titanium oxynitride fine particles, the molar ratio of Ti and N + O varies in the range from 1: 1 to ± 20%. As a result, titanium oxynitride fine particles whose molar ratio deviates from 1: 1 can be applied.

Weak reducing titanium oxide fine particles are fine particles of titanium oxide weak reducing titanium oxide obtained by the mild reducing treatment _{(TiO 2) (TiO 2-} x). Specific examples of the composition include those in the range of 0.02 ≦ x ≦ 0.8 in the composition formula represented by TiO _2-x . Specific examples of the composition include dititanium trioxide (Ti ₂ O ₃ ), tetratitanium trioxide (Ti ₄ O ₇ ), a mixed crystal thereof, and a mixture thereof.
As the above-described 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 diameter of titanium compound fine particles such as titanium oxide fine particles, titanium oxynitride 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. Clear light transmittance can be obtained in a colored layer and a colored substrate described later, without causing light scattering in the region.
On the other hand, if the particle diameter is 1 nm or more, the production is easy.
These titanium compound fine particles are all inorganic compounds and have high weather resistance.

(2) Carbon Black Fine Particles As the carbon black fine particles according to the present invention, it is preferable that the nitrogen adsorption specific surface area (BET value) is large and the particle diameter is small because the concealing power becomes strong and the dispersibility is improved. From this viewpoint, the particle size of the carbon black fine particles is preferably 100 nm or less and 50 nm or less, and more preferably 30 nm or less.
On the other hand, if the particle diameter is 1 nm or more, the production is easy.
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 resin coating treatment.
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. And the said solvent can be selected according to resin mix | blended with the said ink. Specifically, common solvents such as water, alcohol, ether, ester, ketone, and aromatic compound can be used. One or more solvents selected from these solvents can be used.
If necessary, an acid or alkali may be added to the solvent to adjust the pH of the solvent.

(4) Dispersant The dispersant according to the present invention includes the titanium compound fine particles and carbon black fine particles according to the present invention described above in the solvent described above, in a resin used for a colored film described later, in a coating resin, or an adhesive. Used to disperse uniformly into the inside.
As the dispersant, for example, a phosphate ester compound, a polymer dispersant, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, and the like can be preferably used. Examples of the polymer dispersant include acrylic polymer dispersants, urethane polymer dispersants, acrylic / block copolymer polymer dispersants, polyether dispersants, and polyester polymer dispersants. . In addition, a dispersing agent is not limited to these, Various dispersing agents 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 titanium compound fine particles and carbon black fine particles to suppress aggregation of the fine particles, and the fine particles are uniformly distributed in a solvent, a colored film, a coating resin, or an adhesive. Has the effect of dispersing.

  The addition amount of the dispersant is desirably in the range of 10 to 2000 parts by weight, more preferably in the range of 30 to 1000 parts by weight with respect to 100 parts by weight of the fine particles. If the added amount of the dispersant is in 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 the base film. This is because the physical properties of the coating layer, transparent substrate, and pressure-sensitive adhesive layer are not adversely affected.

(5) Infrared absorbing compound As described above, the ink, the dispersion, the colored layer, the colored film, the colored base material, and the colored matching base material according to the present invention have sufficient absorbing ability 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 near-infrared absorption ability, an infrared-absorbing compound having strong absorption in the near-infrared region is optionally applied to inks, dispersions, colored layers, colored films, colored substrates, and colored matching substrates. Further, it may be added. The infrared absorbing compound is roughly classified into an infrared absorbing organic compound and inorganic infrared absorbing fine particles. Hereinafter, the infrared absorbing organic compound and the inorganic infrared absorbing fine particles will be described.

(I) Infrared absorbing organic compound 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, azo compounds. Compounds, pentadiene compounds, azomethine compounds, squarylium compounds, organometallic complexes, cyanine compounds and the like can be used.

(Ii) Inorganic 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. Furthermore, 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 antimony-added tin oxide fine particles, and the tin-added indium oxide fine particles have a concentration that is significantly sufficient to absorb near infrared rays, and the ink, dispersion, colored layer, colored film, Even when added to a colored film, a colored base material, and a colored matching base material, these colors are not significantly affected, which is preferable.

  When inorganic infrared absorbing fine particles are added to the ink, dispersion, colored layer, colored film, colored film, colored substrate, and colored matching substrate according to the present invention at a concentration that is significantly sufficient to absorb near infrared rays However, it is excellent in transparency of visible light and excellent in weather resistance even when used in a harsh environment according to the outdoors or outdoors as a colored board or colored film.

  The inorganic infrared absorbing fine particles can be contained in the ink, the dispersion, the colored layer, the colored film, the colored film, the colored substrate and the colored matching substrate according to the present invention by a known method. For example, an ink is formed by subjecting a composition in which infrared-absorbing fine particles, a solvent, and a dispersant as necessary are mixed to a dispersion treatment. 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 resin constituting the colored base material and to coat the colored base material. A process and an adhesive layer formation process 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 may be selected according to the purpose. it can. Among these, it is preferable to use an ultraviolet curable resin from the viewpoints of hardness, smoothness, fine particle dispersibility, process simplicity, 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 resins, epoxy resins, vinyl ester resins, acrylic resins, and allyl ester resins. . Among these, acrylic resins 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 mainly composed of a photocurable or thermosetting resin can be used. The pressure-sensitive adhesive preferably has durability against ultraviolet rays, and is preferably an acrylic pressure-sensitive adhesive or a silicone pressure-sensitive adhesive. Furthermore, an acrylic adhesive is preferable from the viewpoints of adhesive properties and cost. The acrylic pressure-sensitive adhesive includes a solvent system and an emulsion system. From the viewpoint of easy control of peel strength, a solvent system is preferable. And when using a solution polymerization polymer as an acrylic solvent adhesive, a well-known thing can be used as the acrylic monomer.

(8) Other additives In the ink, the dispersion, the colored layer, the colored film, the colored film, the colored base material, and the colored matching base material according to the present invention, other additives may be added as necessary. Good. For example, in addition to preventing UV deterioration of a colored layer, a colored film, and a colored film by addition of an ultraviolet shielding agent and HALS, ultraviolet rays contained in sunlight are colored substrates, colored alignment substrates, colored films, colored layers, It is possible to suppress intrusion into the vehicle or the room through the colored film and cause light deterioration on human skin, the interior of the vehicle, or the indoor furniture.
Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, cerium oxide fine particles, zinc oxide fine particles, and titanium oxide fine particles.

  Further, for example, by adding an antioxidant, it is possible to prevent deterioration of the colored substrate, the colored layer, and the colored film. In addition, 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 within a range in which the colored substrate or the colored layer maintains a natural color tone.

  About these additives, depending on the effect and desire of the additive, the colored layer and various layers of the colored substrate other than the colored layer, for example, a hard cord layer, a transparent substrate, and an adhesive One or more layers selected from layers and the like can be contained.

(9) Transparent base material The transparent base material used as the base material of the colored base material according to the present invention is preferably a colorless and transparent base material that is transparent to visible light and has little scattering. Specifically, a substrate selected from glass, resin board, and resin film is suitable. When the base material is a resin board or resin film, the types of resin are specifically polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene-vinyl acetate copolymer Examples include coalesced resins, polyester resins, fluororesins, polycarbonate resins, and acrylic resins. Especially, when a base material is a resin film, a polyester resin is preferable and a polyethylene terephthalate resin is especially preferable.

  When the transparent substrate is used, the surface thereof may be subjected to a surface treatment for the purpose of improving the binding property with the resin binder, and typical treatment methods include corona surface treatment, plasma treatment, and sputtering. Examples thereof include discharge treatment such as treatment, flame treatment, metallic sodium treatment, primer layer coating treatment, and the like.

  The transparent substrate 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 by the plurality of transparent base materials to constitute the color matching base material is glass. It is preferable that

(10) Thermoplastic Resin The dispersion according to the present invention can take a form as a colored film such as a sheet, board or film by further containing a thermoplastic resin and molding.
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, fluorine resin, ionomer resin, polycarbonate resin, acrylic resin Resin etc. are mentioned.

[2] Forms of Ink, Dispersed Powder and Masterbatch and Manufacturing Method Thereof Hereinafter, (1) Ink Form and (2) Ink Manufacturing Method will each be described to constitute a dispersion (3) Dispersed Powder and Master The form of the batch, and (4) the dispersion powder and the method for producing the master batch 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 as desired. contains.

By incorporating a coating resin and 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 on a colored substrate.
On the other hand, for example, an ink containing titanium compound fine particles, carbon black fine particles, and an adhesive in the ink can be used as an adhesive layer forming liquid.

The ink according to the present invention has an optical property of a colored substrate obtained by forming a coating layer or a pressure-sensitive adhesive layer on a transparent substrate using the ink, and has JIS Z 8701: 1999 and JIS Z 8729: 2004. In the L * a * b * color value calculated based on the D65 light source and the 10-degree field of view, the value of a * and b * of at least one of the transmission color coordinates or the reflection color coordinates is expressed by 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 and the carbon black fine particles contained in the ink is in the range of [titanium compound fine particles] / [carbon black fine particles] = 100: 10 to 100: 100, The colored base material in which the coating layer and / or the pressure-sensitive adhesive layer is formed on the transparent base material using the ink according to the present invention can satisfy the optical characteristics described above.

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

In particular, on a transparent substrate using an ink containing titanium compound fine particles and carbon black fine particles 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.
The ink 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.

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 value calculated in the light source / 10-degree field of view, the value of at least one of the transmitted color coordinates or the reflected color coordinates is represented by the formula 0 ≦ ((a *) ² + The significance of satisfying (b *) ² ) ^0.5 ≦ 3, more preferably the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2, will be described.
In addition, the significance of the said optical characteristic is the same also about the optical characteristic of the colored layer and colored base material which concern on this invention mentioned later.

When a sample to be measured has a color tone L ^* , a ^* , b ^* with respect to a standard sample having a predetermined color tone L ^* ₀ , a ^* ₀ , b ^* ₀ , it depends on the degree of kneading and color gamut of the observer Although there is a case, the color difference ΔE = ((ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ) ^1/2 = ((L ^* −L ^* ) specified in JIS Z 8730: 2009 _{^{0) 2 + (a * -a}} * 0) 2 + (b * -b * 0) 2) When ^half the value is 0 to 3, visually the difference in color tone between the standard sample and the target sample It is difficult to discriminate with. In particular, if the color difference ΔE is 0 or more and 2 or less, it is further difficult to discriminate.
On the other hand, when the standard sample has an ideal gray color tone and 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 simultaneously satisfying the above, the color difference of the sample to be measured with respect to the standard sample is calculated as 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 an ideal gray color tone satisfies the expression 0 ≦ ((a ^* ) ² + (b ^* ) ² ) ^1/2 ≦ 3, It is difficult to visually determine the difference in color tone between a standard sample having a color tone and a sample to be measured. This is because it is more difficult to discriminate when the relationship of the expression 0 ≦ ((a ^* ) ² + (b ^* ) ² ) ^1/2 ≦ 2 is satisfied.
As a result, a colored layer or a colored substrate having a natural color tone can be produced by using the ink according to the present invention.

(2) Method for Producing Ink The ink according to the present invention can be produced by a known method.
During the production, the ink according to the present invention can be produced by adding titanium compound fine particles and carbon black fine particles to a solvent that is a liquid medium at a predetermined ratio and performing dispersion treatment on both fine particles simultaneously. I can do it. Further, after the dispersion of the titanium compound fine particles and the dispersion of the carbon black fine particles are produced by separate dispersion treatments, the two types of dispersions are mixed at a predetermined ratio, whereby the ink according to the present invention. May be manufactured.
The method for 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, ball mill, sand mill, ultrasonic dispersion, or the like can be used.

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

The infrared absorbing compound, coating resin, pressure-sensitive adhesive, and other additives described above 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 using inorganic infrared-absorbing fine particles as the infrared-absorbing compound or using inorganic ultraviolet-absorbing fine particles as the ultraviolet absorber, a dispersion of these fine particles is prepared in advance, The ink is preferably added 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 be lowered. Therefore, it is preferable to add the coating resin and the pressure-sensitive adhesive to the dispersion liquid after the titanium compound fine particles and / or the carbon black fine particles are dispersed.

(3) Forms of dispersed powder and master batch 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 powder form, and the master batch has a pellet form.

  By mixing the dispersed powder and master batch 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, film or board obtained by dispersing titanium compound fine particles and carbon black fine particles in a thermoplastic resin using the dispersed powder and masterbatch. The optical characteristics of the colored film having a form can be considered in the same manner as the ink described above.

(4) Manufacturing method of dispersed powder and masterbatch The dispersed powder and masterbatch which concern on this invention can be manufactured by a well-known method.
For example, by removing a volatile component such as an organic solvent from the above-mentioned dispersion liquid, a dispersion powder that is a powdery dispersion in which titanium compound fine particles and carbon black fine particles are dispersed at a high concentration in a dispersant can be obtained. . The method for removing the volatile component 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 component. Examples of the apparatus used for the reduced-pressure drying include a vacuum agitation type dryer, but any apparatus having the above functions may be used, and there is no particular limitation. Further, the pressure value at the time of drying under reduced pressure is not particularly limited and can be appropriately selected.
When removing volatile components from the dispersion, the solvent removal efficiency from the mixture can be improved by using a vacuum drying method. Further, since the dispersion is not exposed to high temperature for a long time, the titanium compound fine particles and the carbon black fine particles dispersed in the dispersion are not aggregated, which is preferable. Furthermore, it is easy to recover the evaporated solvent, which is preferable from the viewpoint of environmental considerations.
In addition, by dispersing the dispersed powder in a resin and molding the resin into a pellet, a pellet-like dispersion, that is, a master batch can be obtained.

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

[3] Colored Layer, Colored Substrate, Colored Film, Colored Matching Substrate, and Method for Producing the Same Hereinafter, including descriptions of the colored layer and the colored film, (1) Form of the colored layer, (2) Form of the colored substrate , (3) Colored film and colored matching substrate, (4) Colored layer and colored substrate manufacturing method, (5) Colored film and colored matching substrate manufacturing method, respectively.

(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. Based on JIS Z 8701: 1999 and JIS Z 8729: 2004, a D65 light source at 10 degrees. In the L * a * b * color value calculated in the field of view, the value of a * and b * of at least one of the transmission color coordinates or the reflection color coordinates is expressed by the formula 0 ≦ ((a *) ² + (b * ² ) It is characterized by satisfying ^0.5 ≦ 3.

When manufacturing the colored base material which concerns on this invention using the colored layer of this invention, it is preferable that the visible light transmittance | permeability calculated by JISR3106: 1998 is 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 secured. Moreover, if it is 60% or less, the transmittance of the colored base material with respect to human visibility will be appropriate, and the role of the colored base material will prevent dazzling of vehicle passengers due to sunlight, and comfort in the vehicle and the interior of the vehicle. This is because it is possible to secure the effects of improving the performance, improving the cooling efficiency and the automobile fuel consumption, and protecting the privacy by blocking the human eyes.
From this viewpoint, the visible light transmittance of the colored substrate is more preferably 0.5% or more and 40% or less.

Using the colored layer and ink according to the present invention, for example, when used for a black matrix formed between pixels of a display, etc., by increasing the total weight of titanium compound fine particles and carbon black fine particles per unit projected area, 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 transmittance, while the reflection color satisfies ΔE = ((a *) ² + (b *) ² ) ^0.5 ≦ 3, preferably ΔE = (( 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 substrate such as glass, a resin sheet, or a resin film using the ink, a coating film having a deep black color and a natural color tone is obtained. That is, the ink can be used as a paint, and the colored layer can be used as a black matrix formed between pixels of the 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, similarly to the colored layer having a visible light transmittance of 0.2% to 60%. L * a * b * color tone calculated with a D65 light source and a 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004 In a value, the ratio of at least one of the transmission color coordinates or the reflection color coordinates a * and b * satisfies the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 3. And titanium compound fine particles and carbon black fine particles.
Further, the colored layer is a dispersion according to the present invention, the total weight of the titanium compound particles and carbon black compound fine particles contained in the per unit projected area is 0.05 g / m ² or more 1.50 g / m ² or less It is preferable.

Specifically, the weight ratio of titanium compound fine particles and carbon black fine particles contained in the coating layer or pressure-sensitive adhesive layer which is the dispersion according to the present invention and is a colored layer is [titanium compound fine particles] / [carbon Black fine particles] When the titanium compound fine particles are less than the value of 100: 10, it is possible to prevent the color of the colored base material from shifting from gray showing a natural color tone to blue to blue purple. As a result, ΔE = ((a *)) ² + (b *) ² ) ^0.5 ≦ 3, which makes it easy to satisfy the optical characteristics described above.
On the other hand, since the amount of carbon black fine particles is less than the value of the above-mentioned [titanium compound fine particles] / [carbon black fine particles] = 100: 100 weight ratio, the color of the colored base material changes from gray showing a natural color tone to brown. You can avoid to stop. As a result, ΔE = ((a *) ² + (b *) ² ) ^0.5 ≦ 3, which makes it easy to satisfy the optical characteristics described above.
In particular, a more natural color tone is realized by containing titanium compound fine particles and carbon black fine particles in a ratio satisfying the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2. Which is particularly preferred.

The colored layer according to the present invention is not limited to the above-described uses such as paint, black matrix, and colored base material. For example, sunglasses, laser protective glasses, a neutral density filter or ND filter as an optical element, a light shielding film for agriculture, food It can also be applied to protective films.
The colored layer 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.

(2) Form of colored substrate The colored substrate according to the present invention has a transparent substrate containing at least titanium compound fine particles and carbon black fine particles, or a coating layer or an adhesive layer on at least one side of the transparent substrate. It is a colored substrate. And at least one layer of the coating layer or the pressure-sensitive adhesive layer is a colored layer, and the colored base material is 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 value, the value of a * and b * of at least one of the transmission color coordinates or the reflection color coordinates is expressed by the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 It is characterized by satisfying ≦ 3.
In particular, by adding the titanium compound fine particles and the carbon black fine particles to the colored layer at a ratio satisfying the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2, it becomes more natural. A color tone can be realized, 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. 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 dispersed in the same layer of either the coating layer or the pressure-sensitive adhesive layer.

  The titanium compound fine particles and the carbon black fine particles are more preferably contained in the coating layer than the pressure-sensitive adhesive layer. This is because when the titanium compound fine particles or carbon black fine particles are contained in the pressure-sensitive adhesive layer, when the colored film according to the present invention is applied to a window or the like, the pressure-sensitive adhesive film thickness is uniform in the plane. This is because there is a possibility that uneven color may occur when the amount of fine particles per area changes.

  In addition, in the colored film which has an adhesive layer, it is also preferable to laminate | stack a release film on the adhesive layer surface from a practical viewpoint. In addition, a film that is easily softened by heat, such as a dryer, may be used as a base film so that it can be easily attached to a curved surface like a back window of an automobile.

Here, it is preferable to form a coating layer on at least one surface of the film substrate using a coating resin even when the adhesive layer is configured to include both titanium compound fine particles and carbon black compound fine particles. It is a configuration.
This is because an appropriate coating layer is formed on the surface of the film substrate, so that practical properties such as weather resistance and surface scratch resistance of the colored film substrate are improved.

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 appropriately controlled by controlling the weight ratio between the fine particles in the ink and 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 since both the titanium compound fine particles and the carbon black fine particles are inorganic compounds.

(3) Form of colored film and colored matching base material The colored film according to the present invention contains a thermoplastic resin and can be formed into a sheet shape, a board shape, a film shape, or the like by being molded. .
A known method can be applied as the molding method.
One or more selected from the above-described colored layer and colored film-colored base material are arranged between a plurality of transparent base materials, or are sandwiched by a plurality of transparent base materials, thereby providing a colored matching base material according to the present invention. It becomes.
Moreover, it is preferable that the transparent base material for comprising a coloring matching base material is glass.

The colored film and the color matching substrate according to the present invention are themselves L * a * b * colors calculated with a D65 light source and a 10-degree field of view based on JIS Z 8701: 1999 and JIS Z 8729: 2004. In the values, the value of a * and b * of at least one of the transmission color coordinates or the reflection color coordinates satisfies the expression 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 3.
In particular, by adding the titanium compound fine particles and the carbon black fine particles to the colored layer at a ratio satisfying the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2, it becomes more natural. A color tone can be realized, which is particularly preferable.

  In addition, about the optical characteristic and manufacturing conditions of the coloring matching base material which concern on this invention, it can consider similarly to the colored layer and coloring base material which were mentioned above.

(4) Manufacturing method of colored layer and colored substrate The colored layer according to the present invention can be formed using the coating ink according to the present invention or the pressure-sensitive adhesive layer forming liquid according to the present invention.
The colored substrate according to the present invention can be produced using the transparent substrate and the coating ink according to the present invention, or the transparent substrate and the adhesive layer forming liquid according to the present invention.

Hereinafter, the manufacturing method of a colored layer and a colored base material will be specifically described using an example of a manufacturing process of 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, after coating the transparent film substrate surface with the coating ink according to the present invention, the solvent is evaporated. Then, by curing the coating resin by a predetermined method, a coating layer which is a colored layer in which the titanium compound fine particles and the carbon black fine particles are dispersed in the coating resin is formed on the surface of the transparent film substrate, and the colored film according to the present invention Can be manufactured.

  In addition, after the adhesive layer forming liquid according to the present invention is coated on the surface of the transparent film substrate, the solvent is evaporated, whereby the pressure-sensitive adhesive layer is also a colored layer in which the titanium compound fine particles and the carbon black fine particles are dispersed in the medium. A colored film according to the present invention can be produced on the surface of a transparent substrate.

  When the coating layer or the pressure-sensitive adhesive layer is provided on the transparent film substrate, the method for applying the coating ink according to the present invention may be any method that can uniformly apply the ink to the surface of the transparent film substrate. It is not limited. Examples thereof include a bar coating method, a gravure coating method, a spray coating method, and a dip coating method.

  Here, as a method for producing a colored film, in the coating ink according to the present invention using an ultraviolet curable resin as a coating resin, the coating layer is formed using the bar coating method as an example. 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 an appropriate leveling property. And the coating film of the said ink can be formed on a base film using the wire bar of a suitable bar number according to the thickness of a desired coating layer, and content of the microparticles | fine-particles in a coating layer. Next, after removing the solvent contained in the applied ink by drying, the coating layer can be formed on the transparent film substrate by irradiating with ultraviolet rays and curing.
At this time, the drying condition of the coating film of the coating ink varies depending on the components contained in the coating ink, the type of solvent, and the use ratio, but for example, at a temperature of 60 ° C. to 140 ° C. for about 20 seconds to 10 minutes. By heating, the coating film of the coating ink can be dried.
Moreover, the ultraviolet irradiation method is not particularly limited, and for example, a UV exposure machine such as an ultra-high pressure mercury lamp can be suitably used.

In addition to the above operations, before and after the above-described coating layer forming step, further appropriate steps are carried out, adhesion between the transparent film substrate as a substrate and the coating layer, smoothness of the coating film during coating, solvent It is also possible to manipulate the dryness of the. Examples of the step optionally performed before and after the coating layer forming step include a substrate surface treatment step, a pre-bake (base film pre-heating) step, and a post-bake (base film post-heating) step. Can be appropriately selected. When performing a pre-baking process and / or a post-baking process, it is preferable that the heating temperature in the said process is 80 to 200 degreeC, for example, and heating time is 30 second-240 second.
Although the thickness of the coating layer on a transparent film base material is not specifically limited, It is preferable that it is 10 micrometers or less, and it is more preferable that it is 6 micrometers or less. If the thickness of the coating layer is 10 μm or less, in addition to exhibiting sufficient pencil hardness and scratch resistance, the transparent film base material is used for solvent evaporation and binder curing in the coating layer. This is because the occurrence of process abnormalities such as the occurrence of warpage can be suppressed.

(5) Colored film, method for producing a colored matching substrate The colored matching substrate according to the present invention is selected from a colored layer, a colored film having a form of a sheet, board or film according to the present invention, and a colored substrate. One or more kinds to be produced can be produced by arranging them between a plurality of transparent substrates or sandwiching them between a plurality of transparent substrates.
Hereinafter, an example of a method for producing a colored film and a colored matching substrate will be specifically described using an example of a process for producing a colored film and a colored matching substrate according to the present invention. However, the present invention is limited to this description. It is not something.
The thermoplastic resin contained in the colored film used as the intermediate layer of the color matching substrate is made of polyvinyl acetal resin or ethylene / vinyl acetate copolymer from the viewpoint of adhesion to a transparent substrate, weather resistance, penetration resistance, etc. Preferably, it is a polyvinyl butyral resin.

Further, when the thermoplastic resin constituting the colored film alone does not have sufficient flexibility and adhesion to a transparent substrate, for example, when the thermoplastic resin is a polyvinyl acetal resin, a plasticizer is further added. It is preferable.
As a plasticizer, the substance used as a plasticizer with respect to the thermoplastic resin which concerns on this invention can be used. For example, as a plasticizer used for a heat ray shielding film composed of a polyvinyl acetal resin, a plasticizer that is a compound of a monohydric alcohol and an organic acid ester, a plasticizer that is an ester system such as a polyhydric alcohol organic acid ester compound, Examples include phosphoric acid plasticizers such as organic phosphoric acid plasticizers. Any plasticizer is preferably liquid at room temperature. Among these, a plasticizer that is an ester compound synthesized from a polyhydric alcohol and a fatty acid is preferable.

After kneading a powder or pellet dispersion, a thermoplastic resin, and, if desired, a plasticizer and other additives, the kneaded product is formed into a film by a known method such as an extrusion molding method or an injection molding method. A colored film can be produced.
A known method can be used for forming the film-like colored layer. For example, a calendar roll method, an extrusion method, a casting method, an inflation method, or the like can be used.
The colored matching substrate according to the present invention can be obtained by interposing the thus produced film-like colored film as an intermediate layer between a plurality of transparent substrates made of a sheet glass or plastic material. In addition, in a method for obtaining a laminated base material by interposing a film-like dispersion between a plurality of transparent base materials, a known laminating method can be used.

EXAMPLES Hereinafter, although this invention is demonstrated concretely, referring an Example, this invention is not necessarily limited to these Examples.
In Examples and Comparative Examples, the optical properties of the colored film were measured using a spectrophotometer U-4100 (manufactured by Hitachi, Ltd.).
Specifically, the following procedure is followed.
(1) The spectral transmittance (dependence of transmittance on the light wavelength) of the sample is measured with a spectrophotometer.
(2) Based on JIS Z 8701, the measured spectral transmittance is converted into an X ₁₀ Y ₁₀ Z ₁₀ color value with a D65 light source and a 10 ° field of view.
(3) The converted X ₁₀ Y ₁₀ Z ₁₀ color value is converted into an L * a * b * color value in a D65 light source and 10 ° field of view based on JIS Z 8729, and a *, b * Get the value of.

As the film substrate, transparent PET film HPE-50 (manufactured by Teijin Limited, thickness 50 μm) (hereinafter simply referred to as “PET film”) was used. When the optical properties of the PET film were measured, the visible light transmittance was 89.2%, and the solar radiation transmittance was 89.2%. Further, a * = 0.0 and b * = 0.8 in the color coordinates, and the value of the color difference ΔE = ((a *) ² + (b *) ² ) ^0.5 from gray is 0.8. It was. This is shown in Table 1. The spectral transmittance of the PET film is shown in FIG. 1 and FIG. 2 using a thin solid line.

Example 1
Acrylic polymer dispersant having 10% by mass of titanium nitride fine particles (average particle size 30 nm) and a group containing amine as a functional group (an amine dispersant having an amine value of 48 mgKOH / g and a decomposition temperature of 250 ° C.) (hereinafter, Abbreviated as Dispersant a.) 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 (hereinafter abbreviated as dispersion A).

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 were weighed. 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 (hereinafter abbreviated as dispersion B).

  Dispersion A and Dispersion B were mixed so that the weight ratio of titanium nitride fine particles and 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 the mixed ink, 100 parts by weight of an ultraviolet curable resin (Aronix UV-3701 manufactured by Toagosei Co., Ltd., an acrylic ultraviolet curable resin having an active ingredient of 100%, hereinafter simply referred to as an ultraviolet curable resin) and toluene. After adding 800 parts by weight, the mixture was 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. The coating ink A was formed into a film by a bar coater using a wire bar No. 6. This 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. Thus, 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 colored 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%. Further, in color coordinates, a * = − 1.1, b * = 0.2, and the color difference from gray ΔE = ((a *) ² + (b *) ² ) ^1/2 was 1.1. . This is shown in Table 1.

(Examples 2 to 6)
A colored film according to Examples 2 to 6 (hereinafter referred to as Colored Film B, Colored Film C, and Colored Film, respectively) in the same manner as Example 1 except that the coating film thickness was changed by changing the bar number of the wire bar. D, abbreviated as colored film E, and colored film F).
In Example 2, no. 10, No. 3 in Example 3. 12, No. 4 in Example 4. 18, No. 5 in Example 5. 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 displayed together with the total weight of the colored materials per unit projected area included in the colored film. It was shown in 1.

(Example 7)
Dispersion A and Dispersion B produced in Example 1 were mixed so that the weight ratio of titanium nitride fine particles to carbon black fine particles contained in the ink was 100: 50. By adding 100 parts by weight of UV curable resin and 800 parts by weight of toluene to 100 parts by weight of the mixed ink, the inks for coating according to Example 7 (hereinafter abbreviated as coating ink G) are mixed thoroughly. ).

  On the surface of the PET film, no. Using the wire bar No. 4, the coating ink G was formed into a film by a bar coater. This 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. 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 material 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 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.
And the optical characteristic of the colored film H was measured similarly to Example 1, and it showed in Table 1 with the total weight of the colored material per unit projection area contained in a colored film.

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

  On the surface of the PET film, no. Using the wire bar No. 3, the coating ink I was formed into a film with a bar coater. This 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) in which a coating layer containing titanium nitride fine particles and carbon black fine particles was formed was obtained. 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 material per unit projected area contained in the colored film.

(Example 10)
Dispersion A and Dispersion B produced in Example 1 were mixed so that the weight ratio of titanium nitride fine particles to carbon black fine particles contained in the ink was 100: 25. After adding 100 parts by weight of UV curable resin and 800 parts by weight of toluene to 100 parts by weight of this mixed ink, the ink for coating according to Example 10 (hereinafter referred to as “coating ink J”) is mixed thoroughly. Abbreviated).

  On the surface of the PET film, no. Using the wire bar No. 4, the coating ink J was formed by a bar coater. This 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. Thus, 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. 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 material per unit projected area contained in the colored film.

(Examples 11 to 13)
A colored film according to Examples 11 to 13 (hereinafter referred to as a colored film K, a colored film L, and a colored film, respectively) in the same manner as in Example 10 except that the coating film thickness was changed by changing the bar number of the wire bar. Abbreviated as M). In Example 11, no. 10 and Example 12, no. 12, No. 13 in Example 13. Sixteen wire bars were used.
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 material per unit projected area included in the colored film.

(Example 14)
Dispersion A and Dispersion B produced in Example 1 were mixed so that the weight ratio of titanium nitride fine particles to 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, the mixture ink is sufficiently mixed, whereby the coating ink according to Example 14 (hereinafter abbreviated as coating ink N) is obtained. ).

  On the surface of the PET film, no. Using the wire bar No. 4, the coating ink N was formed by a bar coater. This 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. Thus, a colored film according to Example 14 (hereinafter abbreviated as “colored film N”) in which a coating layer containing titanium nitride fine particles and carbon black fine particles was formed was obtained. 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 material 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. 6 wire bars were used.
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 material per unit projected area contained in the colored film.

(Example 16)
Dispersion A and Dispersion B produced in Example 1 were mixed so that the weight ratio of titanium nitride fine particles to carbon black fine particles contained in the ink was 100: 10. To 100 parts by weight of the mixed ink, 100 parts by weight of an ultraviolet curable resin and 800 parts by weight of toluene were added and then mixed sufficiently, whereby the coating ink according to Example 16 (hereinafter abbreviated as coating ink P). ).

  On the surface of the PET film, no. Using the wire bar No. 4, the coating ink P was formed into a film by a bar coater. This 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. 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 material per unit projected area contained in the colored film.

(Example 17)
10% by mass of antimony-doped tin oxide (ATO) fine particles (average particle size 24 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 10 hours to obtain an ATO fine particle dispersion (hereinafter abbreviated as dispersion C).

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

  On the surface of the PET film, no. The coating ink Q was formed into a film by a bar coater using 10 wire bars. This 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. Thus, 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. 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 material per unit projected area contained in the colored film.

(Example 18)
10% by mass of titanium oxynitride fine particles (average particle size 28 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 15 hours to obtain a titanium oxynitride fine particle dispersion (hereinafter abbreviated as dispersion D).

  Dispersion D and dispersion A prepared in Example 1 were mixed so that the weight ratio of titanium oxynitride fine particles and carbon black fine particles contained in the ink was 100: 50. To 100 parts by weight of the mixed ink, 100 parts by weight of an ultraviolet curable resin and 800 parts by weight of toluene were added and then mixed sufficiently, whereby the coating ink according to Example 18 (hereinafter abbreviated as coating ink R). ).

  On the surface of the PET film, no. The coating ink R was formed into a film by a bar coater using a wire bar No. 6. This 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. Thus, a colored film according to Example 18 (hereinafter abbreviated as “colored film R”) in which a coating layer containing titanium oxynitride fine particles and carbon black fine particles was formed was obtained. 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 material per unit projected area contained in the colored film.

(Examples 19 to 22)
Colored films according to Examples 19 to 22 (hereinafter referred to as Colored Film S, Colored Film T, and Colored Film, respectively) in the same manner as Example 18 except that the coating film thickness was changed by changing the bar number of the wire bar. U, abbreviated as colored film V). In Example 19, no. 9, No. 20 in Example 20. 10, No. 21 in Example 21. 14, No. 22 in Example 22. 22 wire bars were used.
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 material per unit projected area included in the colored film. .
Further, the spectral transmittance of the colored film V obtained in Example 22 is shown in FIG. 1 and FIG. 2 using a thick solid line.

(Example 23)
Dispersion B prepared in Example 1 and Dispersion D prepared in Example 18 were mixed so that the weight ratio of titanium oxynitride fine particles to carbon black fine particles contained in the ink was 100: 80. To 100 parts by weight of the mixed ink, 100 parts by weight of UV curable resin and 800 parts by weight of toluene were added and then mixed well, whereby the coating ink according to Example 23 (hereinafter abbreviated as coating ink W). ).

  On the surface of the PET film, no. Using the wire bar No. 4, the coating ink W was formed into a film by a bar coater. This 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 oxynitride fine particles and carbon black fine particles was obtained. And the optical characteristic of the colored film W was measured similarly to Example 1, and it showed in Table 1 with the total weight of the coloring material per unit projection area contained in a 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. 5 wire bars were used.
And the optical characteristic of the colored film X was measured similarly to Example 1, and it showed in Table 1 with the total weight of the colored material per unit projection area contained in a colored film.

(Example 25)
Dispersion A and Dispersion 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, Dispersant a was added to the mixed ink. At this time, the ratio of the weight of the dispersant and the combined weight of the titanium nitride fine particles and the carbon fine particles contained in the mixed ink added with the dispersant a is (dispersant weight): ((titanium nitride fine particles The dispersing agent a was added to the mixed ink so that the weight of the fine particles) + (the weight of the carbon fine particles)) = 900: 100.
In addition, (weight of the dispersing agent) in the said formula is the dispersing agent added after mixing the weight of the dispersing agent added at the time of manufacturing the dispersion A and the dispersion B, and the dispersion A and the dispersion B. The total weight is shown.

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

After 99.87 parts by weight of polycarbonate resin powder (manufactured by Teijin) and 0.13 parts by weight of dispersed powder Y were mixed and fed to a twin-screw extruder set at 280 ° C. and kneaded, extrusion molding was performed. Molded into a 1.0 mm thick sheet. This obtained the sheet-like colored film (henceforth the colored film Y) containing the polycarbonate resin which is a thermoplastic resin concerning Example 25.
The total weight of the coloring material per unit projected area included in the coloring film Y was 0.16 g / m ² . Moreover, 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%. Further, in color coordinates, a * = − 1.0, b * = 0.4, and the color difference from gray ΔE = ((a *) ² + (b *) ² ) ^1/2 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 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. and kneaded, and then extruded from a T die and formed into a 0.76 mm thick film by a calender roll method. Thereby, as a thermoplastic resin according to Example 25, a film-like colored film containing a polyvinyl butyral resin (hereinafter, simply referred to as a colored film Z) was produced.

After the produced colored film Z is temporarily sandwiched between two transparent float glasses (3 mm thick), the temporarily sandwiched product is heated to 130 ° C. and subjected to a press treatment for 5 minutes under vacuum to form a colored matching substrate ( Hereinafter, it was abbreviated as a colored matching substrate Z).
The total weight of the coloring material per unit projected area contained in the obtained colored matching substrate Z was 0.16 g / m ² . Moreover, as a result of measuring the optical characteristic of the coloring matching substrate Z, the visible light transmittance was 35.0% and the solar radiation transmittance was 42.6%. Further, in 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)
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 A which is the titanium nitride dispersion prepared in Example 1, Comparative Example 1 was sufficiently mixed. Such a coating ink (hereinafter abbreviated as coating ink α) was obtained.

On the surface of the PET film, no. The coating ink α was formed into a film by a bar coater using 24 wire bars. This 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 containing carbon black fine particles was obtained. The optical properties 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 material per unit projected area contained in the colored film.
The spectral transmittance of the colored film α obtained in Comparative Example 1 is shown in FIG. 1 and FIG.

(Comparative Example 2)
By adding 100 parts by weight of UV curable resin and 800 parts by weight of toluene to 100 parts by weight of dispersion B, which is the carbon black dispersion prepared in Example 1, Comparative Example 2 was sufficiently mixed. The coating ink (hereinafter abbreviated as coating ink β) was obtained.

On the surface of the PET film, no. The coating ink β was formed into a film by a bar coater using 10 wire bars. This 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. Thus, a colored film according to Comparative Example 2 (hereinafter abbreviated as colored film β) in which a coating layer containing carbon black fine particles and not containing titanium nitride fine particles was formed was obtained. 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 material per unit projected area contained in the colored film.
Further, the spectral transmittance of the colored film β obtained in Comparative Example 2 is shown in FIGS. 1 and 2 using long broken lines.

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

100 parts by weight of dispersion E, 100 parts by weight of UV curable resin and 800 parts by weight of toluene were added and mixed well to obtain a coating ink according to Comparative Example 3 (hereinafter referred to as coating ink γ and Abbreviated).
On the surface of the PET film, no. The coating ink γ was formed into a film by a bar coater using 10 wire bars. This 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. Thus, a colored film according to Comparative Example 3 (hereinafter abbreviated as colored film γ) having a coating layer containing a copper phthalocyanine pigment and containing neither titanium nitride fine particles nor carbon black fine particles is obtained. It was. The optical properties 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 material per unit projected area contained in the colored film.
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 (hereinafter abbreviated as Dispersion F).

  Dispersion F and dispersion A prepared in Example 1 were mixed so that the weight ratio of titanium nitride fine particles to iron oxide fine particles contained in the ink was 100: 45. To 100 parts by weight of the mixed ink, 100 parts by weight of UV curable resin and 800 parts by weight of toluene were added and then mixed sufficiently, whereby the coating ink according to Comparative Example 4 (hereinafter abbreviated as coating ink δ). ).

On the surface of the PET film, no. The coating ink δ was formed into a film by a bar coater using 20 wire bars. This 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) in which a coating layer containing titanium nitride fine particles and no carbon black fine particles was formed was obtained. 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 material 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 broken lines.

(Evaluation of Examples 1-26 and Comparative Examples 1-4)
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, the colored film uses only inorganic fine particles having high weather resistance, but ΔE = ((a *) ² + (b *) ² ) ^1/2 is 0 or more and 3 even in a region where the visible light transmittance is low. It had the following natural colors.
Similarly to Examples 1 to 24 described above, the colored films according to Examples 25 and 26, and the color matching substrate according to Example 26 using the same were also formed with titanium compound fine particles and carbon black fine particles at an appropriate ratio. In the same manner, ΔE = ((a *) ² + (b *) ² ) ^1/2 has a natural color tone of 0 or more and 3 or less even in a region where the visible light transmittance is low.

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

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

Since the colored films according to Comparative Examples 1 and 2 contained only one of the titanium nitride fine particles and the carbon black dispersion liquid, they were greatly different from natural colors.
In the colored film according to Comparative Example 3, copper phthalocyanine blue, which is a blue organic pigment, greatly cuts visible light, but because the absorption on the short wavelength side of visible light is not sufficient compared to the long wavelength side of visible light, It was very different from the natural color. Moreover, since copper phthalocyanine blue hardly absorbs in the near-infrared region longer than 780 nm, the solar transmittance is not sufficiently suppressed. For this reason, compared with the colored film which concerns on the Example which has comparable visible light transmittance | permeability, it was a film in which the solar radiation transmittance | permeability was very high and it was inferior in heat-insulating characteristic.
The colored film according to Comparative Example 4 is a combination of titanium nitride fine particles having relatively strong absorption in the visible light long wavelength region and iron oxide fine particles having relatively strong absorption in the short wavelength region of visible light in the same manner as carbon black. It is an example. However, the absorption characteristics of iron oxide have been different from the natural color tone because it cannot have a flat transmittance over the entire visible light region even when combined with titanium nitride. This was the same even when 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 structures of the colored film and the colored layer according to the present invention are epoch-making to solve the above problems. It was.

Claims (36)

Titanium compound fine particles and carbon black fine particles are dispersed in the medium,
A dispersion characterized in that a weight ratio of the titanium compound fine particles to the carbon black fine particles is in a range of [titanium compound fine particles] / [carbon black fine particles] = 100: 10 to 100: 100.   2. The dispersion according to claim 1, wherein the titanium compound fine particles have an average dispersed particle diameter of 1 nm to 100 nm.   The dispersion according to claim 1 or 2, wherein an average dispersed particle size of the carbon black fine particles is 1 nm or more and 100 nm or less.   The dispersion according to any one of claims 1 to 3, wherein the titanium compound fine particles are one or more selected from titanium nitride fine particles, titanium oxynitride fine particles, and weakly reduced titanium oxide fine particles.   The dispersion according to any one of claims 1 to 4, further comprising infrared absorbing fine particles.   6. The infrared absorbing fine particles are at least one 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. The dispersion according to 1.   The dispersion according to any one of claims 1 to 6, wherein the medium is an inorganic binder and / or an organic binder.   The dispersion according to claim 7, wherein the organic binder is at least one selected from an ultraviolet curable resin, a thermosetting resin, an electron beam curable resin, a room temperature curable resin, and a thermoplastic resin.   A colored layer, wherein the dispersion according to any one of claims 1 to 8 is formed on a substrate. The visible light transmittance calculated by the method defined in JIS R 3106: 1998 is 0% or more and 60% or less,
In the L * a * b * color value calculated in JIS Z 8701: 1999 and JIS Z 8729: 2004 with a D65 light source and a 10-degree field of view, at least one of the transmitted color coordinates and the reflected color coordinates a * and b The colored layer according to claim 9, wherein the value of * satisfies the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 3. 11. The colored layer according to claim 11, wherein the values of the color coordinates a * and b * satisfy the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2. Wherein the total weight of the titanium compound particles and carbon black compound fine particles contained in the per unit projected area is 0.05 g / m ² or more 1.50 g / m ² or less, any one of claims 9 11, The colored layer described in 1.   The colored layer according to claim 9, wherein the base material is resin or glass. A molded body of the dispersion according to any one of claims 1 to 8,
A colored film, wherein the molded body has a film shape, a sheet shape, or a board shape. The visible light transmittance calculated by the method defined in JIS R 3106: 1998 is 0% or more and 60% or less,
In the L * a * b * color value calculated in JIS Z 8701: 1999 and JIS Z 8729: 2004 with a D65 light source and a 10-degree field of view, at least one of the transmitted color coordinates and the reflected color coordinates a * and b The colored film according to claim 14, wherein the value of * satisfies the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 3. The colored film according to claim 15, wherein the values of the color coordinates a * and b * satisfy the expression 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2. Wherein the total weight of the titanium compound particles and carbon black compound fine particles contained in the per unit projected area is 0.05 g / m ² or more 1.50 g / m ² or less, any one of claims 14 16, The colored film according to 1.   The colored film according to claim 14, wherein the colored film contains a thermoplastic resin.   The dispersion according to any one of claims 1 to 8, wherein the dispersion is a powder.   It is a dispersion in any one of Claim 1-8, Comprising: The said dispersion is a pellet form, The masterbatch characterized by the above-mentioned.   One or more types selected from the colored layer according to any one of claims 9 to 13 and the colored film according to any one of claims 14 to 18 are provided on a transparent substrate. Characteristic colored substrate. The visible light transmittance calculated by the method defined in JIS R 3106: 1998 is 0% or more and 60% or less,
In the L * a * b * color value calculated in JIS Z 8701: 1999 and JIS Z 8729: 2004 with a D65 light source and a 10-degree field of view, at least one of the transmitted color coordinates and the reflected color coordinates a * and b The colored base material according to claim 21, wherein the value of * satisfies the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 3. The colored base material according to claim 22, wherein the values of the color coordinates a * and b * satisfy the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2. .   The colored substrate according to any one of claims 21 to 23, wherein the transparent substrate is a resin or glass.   Any one selected from the colored layer according to any one of claims 9 to 13, the colored film according to any one of claims 14 to 18, and the colored substrate according to any one of claims 21 to 24. A colored matching substrate, wherein at least seeds are provided between a plurality of transparent substrates. The visible light transmittance calculated by the method defined in JIS R 3106: 1998 is 0% or more and 60% or less,
In the L * a * b * color value calculated in JIS Z 8701: 1999 and JIS Z 8729: 2004 with a D65 light source and a 10-degree field of view, at least one of the transmitted color coordinates and the reflected color coordinates a * and b 26. The colored matching substrate according to claim 25, wherein the value of * satisfies the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 3. 27. The coloring matching group according to claim 26, wherein the values of the color coordinates a * and b * satisfy the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2. Wood.   The colored matching substrate according to any one of claims 25 to 27, 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,
Using said ink, onto a transparent substrate, the total weight of the titanium compound particles and carbon black compound fine particles contained in the per unit projected area is 0.05 g / m ² or more 1.50 g / m ² or less colored layer JIS Z 8701: 1999 and JIS Z 8729 when the visible light transmittance calculated by the method specified in JIS R 3106: 1998 is 0% or more and 60% or less in the optical characteristics of the colored base material formed with JIS Z 3729: In the L * a * b * color value calculated with a D65 light source and a 10-degree field of view based on 2004, the value of a * and b * of at least one of the transmission color coordinates or the reflection color coordinates is expressed by the formula 0 ≦ ( a *) ² + (b *) ² ) Ink satisfying ^0.5 ≦ 3. 30. The ink according to claim 29, wherein the values of the color coordinates a * and b * satisfy the formula 0 ≦ ((a *) ² + (b *) ² ) ^0.5 ≦ 2.   The weight ratio between the titanium compound fine particles and the carbon black fine particles contained in the ink is in the range of [titanium compound fine particles] / [carbon black fine particles] = 100: 10 to 100: 100. Item 31. The ink according to item 29 or 30.   32. The ink according to claim 29, wherein an average dispersed particle diameter of the titanium compound fine particles is 1 nm or more and 100 nm or less.   The ink according to any one of claims 29 to 32, wherein an average dispersed particle diameter of the carbon black fine particles is 1 nm or more and 50 nm or less.   The ink according to any one of claims 29 to 33, wherein the titanium compound fine particles are one or more selected from titanium nitride fine particles, titanium oxynitride fine particles, and weakly reduced titanium oxide fine particles.   The ink according to any one of claims 29 to 34, further comprising infrared absorbing fine particles.   36. 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. The ink described in 1.

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