Coloring resin composition, coloring film, decorative substrate

Abstract

The objective of this invention is to provide a coloring resin composition capable of forming a coloring film with high visible light occlusion and near-infrared transmittance, and thus excellent reflective and transmittance tones. As a solution, this invention proposes a coloring resin composition containing (A) a resin and (B) a coloring material, wherein at least a methylimine pigment and a bisbenzofuranone pigment are contained as the aforementioned (B) coloring material. When the weight of all coloring materials is set to 100 parts by weight, the content of the methylimine pigment is 25 to 80 parts by weight, and the content of the bisbenzofuranone pigment is 20 to 75 parts by weight, and the content of the aforementioned (B) coloring material is 1 to 39 parts by weight relative to the total content of the solid components of 100 parts by weight.

Description

Technical Field

[0001] This invention relates to a coloring resin composition, a coloring film that can be used as a near-infrared light-transmitting shielding film, and a decorative substrate. Prior Technology

[0002] In recent years, various biometric authentication methods have been adopted in smartphones and other information terminals to enhance security. Besides the well-known fingerprint authentication, research on facial and iris authentication has been continuously developing, with near-infrared sensors or cameras used in these methods. Furthermore, in automobiles, near-infrared sensors are used in in-vehicle displays (such as motion sensors) and driver monitoring cameras, while infrared laser sensors are used in LiDAR (Light Detection and Ranging) systems, which serve as sensors for driving environments. These near-infrared sensors or cameras are generally placed in decorative parts or the periphery of the housing of various displays outside the display area. However, because transparent or semi-transparent covers have been used in the past, these sensors or cameras are visible from the outside, which poses a design flaw. Therefore, the industry is researching filters or colored films with high near-infrared transmittance and low visible light transmittance to conceal near-infrared sensors or cameras. Regarding the hue of the reflection from the filter or coloring film, from a design point of view, it is preferable to be similar to the hue of the periphery of the display or housing when it is not lit, and preferably a non-color black.

[0003] Furthermore, in decorative areas outside the display area of ​​in-vehicle displays or in self-illuminating instrument panels, a blackout display method is sometimes used. In this method, the icon appears when the backlight is on and seems not to exist when the backlight is off. To suppress the brightness of the icon when it is lit, or to improve the seamlessness when it is off, a colored film with a visible light transmittance of, for example, 10-80%, is sometimes formed on the icon area. Since the transmitted light when the backlight is on is preferably non-colored, the transmitted hue of the colored film formed for the purpose of blackout icons is preferably non-colored.

[0004] Typically, the colored films used to conceal near-infrared cameras and the colored films used for black-and-white icons are formed from different colored resin compositions. However, with the increasing functionality of in-vehicle displays in recent years, the industry is researching a design that integrates both near-infrared cameras and black-and-white icons within a single display bezel trim. In this case, three decorative layers are required: a colored film for concealing sensor wiring, a colored film for concealing near-infrared cameras, and a colored film for icons. This increases the cost of printing processes or inks. Therefore, the industry desires a process that uses a single colored resin composition to form these three decorative layers.

[0005] For example, the industry has researched a coloring resin composition that uses bisbenzofuranone pigments as coloring materials and sets the crystallite size of the bisbenzofuranone pigments within a specific range (see, for example, Patent Document 1); and a composition for an infrared filter that uses one or more of the group consisting of bisbenzofuranone pigments, imine pigments, and perylene pigments as a near-infrared transmitting black coloring material, and contains 1 to 30% of a coloring material different from the aforementioned near-infrared transmitting black coloring material relative to the total solids (see, for example, Patent Document 2). [Previous Technical Documents] [Patent Literature]

[0006] Patent Document 1: International Publication No. 2019 / 230684 Patent Document 2: Japanese Patent Application Publication No. 2018-120248 Summary of the Invention

[0007] (The problem the invention aims to solve)

[0008] However, the colored film in the technology described in Patent Document 1 has excellent lightfastness, high visible light blocking properties, and high near-infrared transmittance, but its transmittance chromaticity or reflectance is not sufficient. Furthermore, the infrared transmittance filter in the technology described in Patent Document 2 has high visible light blocking properties and less noise from the visible light component, but it does not take into account transmittance chromaticity or reflectance.

[0009] Therefore, the object of the present invention is to provide a coloring resin composition that can form a coloring film with high visible light occlusion and near-infrared transmittance, and further has excellent reflective and transmittance tones. (Technical means to solve the problem)

[0010] Through intensive research, the inventors discovered that by including resin and coloring material in the coloring resin composition, and by including a specific amount of methylimine pigment and bisbenzofuranone pigment as the coloring material, and by setting the content of all coloring materials within a specific range, the above-mentioned problems can be solved, thereby completing the present invention.

[0011] That is, the objective of this invention is mainly achieved through the following structure. A coloring resin composition comprising (A) resin and (B) coloring material, wherein at least a methylimine pigment and a bisbenzofuranone pigment are contained as the (B) coloring material, wherein when the weight of all coloring materials is set to 100 parts by weight, the content of the methylimine pigment is 25 to 80 parts by weight, the content of the bisbenzofuranone pigment is 20 to 75 parts by weight, and the content of the (B) coloring material is 1 to 39 parts by weight relative to the total content of the solid components of 100 parts by weight. (Compared to the effectiveness of previous technologies)

[0012] The coloring resin composition of this invention can produce a coloring film with excellent light transmittance in the near-infrared region (wavelength 800~1000 nm) and light-blocking properties in the visible light region, and further possesses excellent reflective and transmittance tones. Using the coloring resin composition of this invention, excellent near-infrared camera images can be obtained, and a coloring film with a non-color reflective and transmittance tones and good designability can be obtained. Simple Explanation of the Diagram

[0013] Figure 1 shows the X-ray diffraction curve of the colored film obtained by Example 3. Implementation

[0014] The present invention will now be described in further detail.

[0015] The coloring resin composition of the present invention contains (A) resin and (B) colorant. (A) resin acts as a binder in the composition, and (B) colorant improves or adjusts optical properties, particularly the shielding and absorption properties of visible light. The coloring resin composition of the present invention is characterized by containing at least a methylimine pigment and a bisbenzofuranone pigment as the aforementioned (B) colorant. When the total weight of all colorants is set to 100 parts by weight, the content of the methylimine pigment is 25-80 parts by weight, and the content of the bisbenzofuranone pigment is 20-75 parts by weight. Furthermore, in this specification, the "~" indicating a numerical range includes both ends of the value. By containing specific amounts of methylimine pigment and bisbenzofuranone pigment as (B) colorant, and setting the content of all colorants in the total solids within a specific range, a coloring film with neutral reflectance and transmittance can be obtained. Furthermore, by dispersing imine-based and bisbenzofuranone-based pigments at specific crystallite sizes in the coloring resin composition and the colored film, visible light can be blocked, while near-infrared transmittance can be significantly improved. This allows for the acquisition of clear near-infrared camera images through the colored film. Additionally, diffuse reflectance can be suppressed to a lower level, resulting in a more sophisticated and darker colored film. Moreover, by setting the difference between the crystallite sizes of the imine-based and bisbenzofuranone-based pigments within a specific range, visible light blocking can be improved without altering reflectance. The colored film obtained from the colored resin composition of the present invention has a non-color reflectance and transmittance, low diffuse reflectance, and high visible light shielding and high near-infrared transmittance. Therefore, it can be better used as a light shielding film for concealing sensor wiring and / or a light shielding film for concealing near-infrared cameras and / or a light shielding film for blackout mode icons.

[0016] Examples of resins (A) include acrylic resins, Cardo resins, silicone resins, polyimide resins, polyimide precursors, polyurethane resins, polyester resins, and vinyl chloride resins. Two or more of these may also be present. Among these, from the viewpoint of the storage stability of the colored resin composition or the adhesion and reliability of the colored film, acrylic resins, polyurethane resins, or polyester resins are preferred, with acrylic resins being particularly preferred.

[0017] The coloring resin composition of this invention may or may not be photosensitive. By containing an alkali-soluble resin as (A) resin and further containing the following (D) photosensitive agent, photosensitivity can be imparted to the coloring resin composition. Here, an alkali-soluble resin refers to a resin having one or both of hydroxyl and carboxyl groups as alkali-soluble groups, an acid value of 10 mgKOH / g or higher, and a weight-average molecular weight (Mw) of 500 or higher and 150,000 or lower. Here, the weight-average molecular weight (Mw) refers to the value obtained by gel permeation chromatography using tetrahydrofuran as a carrier, converted using a calibration curve obtained from standard polystyrene. Furthermore, the acid value of the alkali-soluble resin refers to the number of mg of potassium hydroxide (unit: mgKOH / g) required to neutralize 1 g of the alkali-soluble resin.

[0018] Examples of alkali-soluble resins include: calomel resins, acrylic resins, phenolic varnish resins, polyimide resins, polyimide precursors, and polybenzo[a]benzene[b]. azole resin, polybenzo[a] Resins containing the aforementioned alkali-soluble groups, such as azole precursors, polyamide resins, and silicone resins. When the coloring resin composition exhibits negative photosensitivity, acrylic resins and polyimide resins are preferred from the viewpoint of pattern processability and coating reliability; from the viewpoint of dispersion stability, resins containing acrylic resins are more preferred. On the other hand, when the coloring resin composition exhibits positive photosensitivity, polyimide resins, polyimide precursors, and polybenzo[a]pyrene resins are preferred from the viewpoint of pattern processability. azole resin, polybenzo[a] Azole precursors and silicone resins; from the viewpoint of pattern processability, resins containing polyimide or polyimide precursors are preferred.

[0019] The coloring resin composition of this invention contains at least a methylimine pigment and a bisbenzofuranone pigment as coloring material (B). When the weight of coloring material (B) is set to 100 parts by weight, it is important to contain 25 to 80 parts by weight of the methylimine pigment and 20 to 75 parts by weight of the bisbenzofuranone pigment. By using specific amounts of methylimine pigment and bisbenzofuranone pigment as coloring material (B) and setting the content of all coloring materials within specific ranges, a coloring film with neutral reflectance and transmittance can be obtained. When the content of the methylimine pigment is less than 25 parts by weight, the transmittance of the coloring film shifts from achromatic to yellow, resulting in a yellowish tint in the transmitted light when backlight is illuminated, which is undesirable. On the other hand, when the content of the methylimine pigment is more than 80 parts by weight, the transmittance of the coloring film shifts from achromatic to blue, resulting in a bluish tint in the transmitted light when backlight is illuminated, which is also undesirable. When the content of bisbenzofuranone pigment is less than 20 parts by weight, the transmittance of the coloring film shifts from achromatic to blue, resulting in a bluish tint in the transmitted light when the backlight is on, which is undesirable. On the other hand, when the content of bisbenzofuranone pigment is more than 75 parts by weight, the transmittance of the coloring film shifts from achromatic to yellow, resulting in a yellowish tint in the transmitted light when the backlight is on, which is also undesirable.

[0020] As for the methylimine-based pigments used in this invention, as long as they have a methylimine structure (RR'C=NR'') (R and R' are independently hydrogen, or an aliphatic or aromatic group that may contain heteroatoms such as nitrogen or oxygen, and R'' is an aliphatic or aromatic group that may contain heteroatoms such as nitrogen or oxygen), they can be used without particular restrictions. Specifically, examples can be found in Japanese Patent Application Publication No. 1-170601 and Japanese Patent Application Publication No. 2-34664, such as "Chromofine Black A1103" manufactured by Dainippon Seika Co., Ltd.

[0021] The bisbenzofuranone pigments used in this invention are pigments having the structure represented by any one of the following general formulas (I) to (III). The structures represented by the following general formulas (I) to (III) are cis-trans isomers, and the bisbenzofuranone pigments may also have two or more compounds containing such structures.

[0022] [Chemistry 1]

[0023] In general formulas (I) to (III), R1 and R2 independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R3 and R4 independently represent R10, OR11, SR11, COR11, CONR11R12, NR11COR12, OCOR11, COOR11, SCOR11, OCSR11, COSR11, CSOR11, CN, a halogen atom, or a hydroxyl group. Among them, R10 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R11 and R12 independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. a and b represent integers from 0 to 4 independently.

[0024] Bibenzofuranone pigments having the structure represented by any of the above general formulas (I) to (III) are known, for example, and can be obtained by the method described in Japanese Patent Publication No. 2012-515233. Furthermore, they are commercially available, for example, as "Irgaphor" (registered trademark) Black S0100CF (trade name, manufactured by BASF).

[0025] Regarding the crystallite size of the pigment contained in the coloring resin composition and the colored film, the crystallite size of the pigment can be calculated by the Scherrer formula shown in the following equation (1) based on the full width at half maximum (FWHM) of the main peak observed in the X-ray diffraction spectrum when CuKα rays are used as the X-ray source.

[0026] [Number 1]

[0027] In equation (1) above, K is a constant of 0.9, and λ is 0.15418 [nm]. β is represented by equation (2) below. θ represents the value of 1 / 2 of the diffraction angle 2θ corresponding to the diffraction peak.

[0028] [Number 2]

[0029] In equation (2) above, βe is the full width at half maximum (FWHM) of the diffraction peak, and βO is the correction value of FWHM (0.13 [°]). Among them, β, βe and βO are calculated in radians.

[0030] X-ray diffraction spectroscopy uses CuKα rays as the X-ray source and performs measurements using wide-angle X-ray diffraction. The X-ray diffraction apparatus used is the DS ADVANCE or an equivalent manufactured by Bruker AXS. Measurement conditions were: output 40 kV / 40 mA, slit system with a div. slit of 0.3°, measurement step (2θ) of 0.0171°, and measurement time of 0.5 seconds per step.

[0031] Regarding the coloring resin composition of the present invention, a film is obtained by coating, drying, and heat-treating the coloring resin composition on a glass substrate. The obtained film is then shaved off. The crystallite size of the imine-based pigment, determined by the full width at half maximum (FWHM) of the main peak obtained through X-ray diffraction spectroscopy, is ideally 10 nm or more and 25 nm or less, and more preferably 10 nm or more and 20 nm or less. This crystallite size is an indicator of the dispersion state of the pigment in the coloring film; the smaller the crystallite size, the more finely dispersed the pigment is in the coloring film. Here, in the case where the resin (A) in the coloring resin composition contains crosslinking groups, the coloring film of the present invention is preferably obtained where the crosslinking groups are thermally and / or photocrosslinked and substantially without residue. This coloring film can be obtained by forming a coating of the coloring resin composition on a transparent substrate, drying the coating by a heating plate or the like, and then heat-treating it by a hot air oven or the like. For example, when the coloring resin composition contains acrylic resin as resin (A), the heat treatment temperature is preferably 170°C or higher, and the heat treatment time is preferably 30 minutes or higher. Furthermore, regardless of the manufacturing conditions of the colored film, the crystallite size in the composition is the same as the crystallite size in the colored film obtained from the composition. When the crystallite size of the imine-based pigment in the colored film is greater than 25 nm, the near-infrared transmittance decreases, and the transmitted scattered light increases, thus reducing the clarity of the infrared camera image obtained by the colored film. Also, because the diffuse reflectance (L* value in SCE) increases in the reflective hue, the blackness of the colored film decreases. To obtain a clearer infrared camera image and a more aesthetically pleasing black reflective hue, it is preferable to set the crystallite size of the imine-based pigment to 20 nm or less. On the other hand, when the crystallite size of the imine-based pigment in the coloring film is less than 5 nm, the dispersion stability of the pigment decreases, which may lead to increased transmitted scattered light or reduced visible light shielding due to pigment reagglomeration. Regarding the crystallite size of the bisbenzofuranone-based pigment in the coloring film, it is preferably 10 nm or more and 25 nm or less, more preferably 10 nm or more and 20 nm or less, similar to that of the imine-based pigment. Regarding the crystallite size of other colorants, it is preferably small, similar to that of the imine-based and bisbenzofuranone-based pigments, preferably within the range of 10 nm or more and 25 nm or less. Furthermore, when the crystallite size of the imine-based pigment is set to α (nm) and the crystallite size of the aforementioned bisbenzofuranone-based pigment is set to β (nm), by setting it to 3.0≦|α-β|≦10.0, the visible light shielding can be improved without changing the reflectivity (L* in SCI).Generally, increasing the content of coloring material in the total solids is a more effective way to improve the visible light opacity of a colored film. However, in this case, the reflected hue of the colored film has a reddish tint, resulting in poor design. As a preferred embodiment of the present invention, it is believed that by setting the difference in crystallite size between methylimine-based pigments and bisbenzofuranone-based pigments as described above, the filling capacity of the coloring material is improved, thereby enhancing the visible light opacity. As a means of setting the crystallite size of the pigment in the colored film to the aforementioned range, it is preferable to ensure that the pigment is stably and uniformly dispersed in a fine state without re-agglomeration in the resin. More specifically, examples include: using pigments with smaller crystallite sizes; or using a bead milling method to manufacture the colored resin composition; etc.

[0032] As coloring material (B), the transmitted and reflected hues of the colored film can be adjusted by including imine-based pigments, bisbenzofuranone-based pigments, and other coloring materials, without inhibiting the effects of the present invention. In this case, it is preferable to include coloring materials with smaller crystallite sizes, similar to imine-based and bisbenzofuranone-based pigments. Examples of coloring materials include commonly used organic pigments, inorganic pigments, and dyes. To improve the heat resistance, reliability, and lightfastness of the colored film, organic or inorganic pigments are preferred.

[0033] Examples of organic pigments include: pyrrolopyrrole dione pigments; azo, diazo, and polyazo pigments; phthalocyanine copper, halogenated phthalocyanine copper, and metal-free phthalocyanine pigments; anthraquinone pigments such as diaminoanthraquinone, diaminodianthraquinone, anthraquinone, styrophenone, anthraquinone, indanthrene, pinanthraphenone, and vioanthraphenone; and quinacridone pigments. Pigments including: pyrene-based pigments; perylene-based pigments; indigo-based pigments; isoindoline-based pigments; isoindoline-based pigments; quinoline-based pigments; anthracene-based pigments; and metal complex-based pigments, etc.

[0034] Examples of inorganic pigments include: titanium dioxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, aluminum white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, iron oxide, molybdenum red, molybdenum orange, molybdenum chrome red, chrome yellow, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, chrome green (viridian), titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine, iron blue, cobalt blue, sky blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet, etc.

[0035] Examples of dyes include: azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigo dyes, carbocation dyes, phthalocyanine dyes, methylene dyes, polymethyl dyes, etc.

[0036] Examples of black organic pigments include carbon black, perylene black, and aniline black. Examples of mixed-color organic pigments include those created by mixing two or more pigments possessing colors such as red, blue, green, purple, yellow, magenta, and cyan to achieve a near-black color. Examples of black inorganic pigments include graphite; microparticles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; and oxides, complex oxides, sulfides, nitrides, and nitrogen oxides of the aforementioned metals.

[0037] Examples of white coloring materials include: titanium dioxide, barium carbonate, zirconium oxide, calcium carbonate, barium sulfate, aluminum white, and silicon dioxide.

[0038] These coloring materials may contain two or more types.

[0039] Regarding the content of (B) colorant, it is important that the content of (B) colorant is 1 to 39 parts by weight relative to 100 parts by weight of the total solid components. Here, the solid components refer to (A) resin, (B) colorant, and (D) photosensitizer and (E) free radical polymerizable compound contained in the resin composition. Furthermore, in the case of components other than these that remain in the film during the preparation of the colored film, these components are also considered solid components. By setting the content of (B) colorant to 1 part by weight or more relative to 100 parts by weight of the total solid components, even for thinner films, visible light blocking properties can be improved. The content of (B) colorant is preferably 10 parts by weight or more relative to 100 parts by weight of the total solid components. On the other hand, by setting the content of (B) colorant to 39 parts by weight or less relative to 100 parts by weight of the total solid components, the reflectance of the colored film can be adjusted to be more achromatic. Furthermore, it can suppress the reflection of incident light at the interface between the colored film and other substrates, thereby further improving near-infrared transmittance. Regarding (B), the content of the coloring material relative to the total content of the solid components in 100 parts by weight is preferably set to 35 parts by weight or less as an upper limit.

[0040] Regarding improved coatability, the coloring resin composition of the present invention preferably contains (C) organic solvent. (C) organic solvent has the function of uniformly dissolving or dispersing (A) resin and (B) colorant. Furthermore, (C) organic solvent is preferably a compound with a boiling point of 110-250°C or lower at atmospheric pressure. Regarding the coloring resin composition of the present invention, coating methods such as rotary coating, slot coating, screen printing, inkjet printing, gravure printing, or rod coating are contemplated. Therefore, if the boiling point is below 110°C, the organic solvent dries quickly, and coating uniformity is prone to abnormalities. On the other hand, if the boiling point exceeds 250°C, organic solvent residue may remain in the obtained colored film, resulting in decreased chemical resistance of the colored film.

[0041] Examples of organic solvents (C) include ethers, acetates, esters, ketones, aromatic hydrocarbons, acetamides, alcohols, etc.

[0042] Examples of ethers include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Examples of acetates include: butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (hereinafter "PGMEA"), dipropylene glycol methyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, etc. Examples of esters include: methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and other lactic acid alkyl esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxypropionate, ethyl hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-hydroxybutyrate, etc. Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Examples of aromatic hydrocarbons include toluene and xylene. Examples of acetamides include N-methylpyrrolidone, N,N-dimethylmethacinamide, and N,N-dimethylacetamide. Examples of alcohols include butanol, isobutanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol. These may also contain two or more of these compounds.

[0043] Of these, acetates are preferred for stabilizing the dispersion of the coloring material. When the weight of the organic solvent (C) is set to 100 parts by weight, the content of acetates is preferably 40 to 100 parts by weight, more preferably 70 to 100 parts by weight.

[0044] When the weight of the coloring resin composition of the present invention is set to 100 parts by weight, from the viewpoint of uniformity of film thickness of the coating film in the coating step, the content of (C) organic solvent is preferably 50 parts by weight or more, and more preferably 70 parts by weight or more. On the other hand, from the viewpoint of suppressing pigment precipitation, the content of (C) organic solvent is preferably 95 parts by weight or less, and more preferably 90 parts by weight or less.

[0045] The coloring resin composition of the present invention contains an alkali-soluble resin as (A) resin and further contains a (D) photosensitizer, thereby imparting photosensitivity. It can possess so-called negative photosensitivity, that is, by exposing the pattern of the dielectric exposure mask, the alkali solubility of the exposed area is reduced, and the unexposed area is removed by an alkaline developer to form the pattern; or it can possess so-called positive photosensitivity, that is, by exposing the pattern of the dielectric exposure mask, the alkali solubility of the exposed area is higher than that of the unexposed area, and the exposed area is removed by an alkaline developer to form the pattern. In the present invention, since it is easier to form a pattern with higher resolution even when the light-blocking properties are high, negative photosensitivity is preferred.

[0046] By using a photopolymerization initiator as a (D) photosensitizer and further containing an (E) radical polymerizable compound, negative photosensitivity can be imparted, that is, the exposed portion is photocured through a radical polymerization reaction. Preferably, the (E) radical polymerizable compound is a compound having two or more radical polymerizable groups.

[0047] Photopolymerization initiators are compounds that generate free radicals through bond breaking and / or reactions caused by exposure. By containing photopolymerization initiators, (E) free radical polymerizable compounds can be photocured through exposure.

[0048] Examples of photopolymerization initiators include carbazole-based photopolymerization initiators, phosphonium oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and α-amine alkyl phenyl ketone-based photopolymerization initiators. Two or more of these may also be included. Among these, carbazole-based photopolymerization initiators and oxime ester-based photopolymerization initiators are preferred for the following exposure steps, in terms of higher sensitivity to mixed rays including i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm).

[0049] From the perspective of improving the sensitivity to exposure, the content of photopolymerization initiator is preferably 1% by weight or more relative to the total content of alkali-soluble resin and (E) radical polymerizable compound.

[0050] On the other hand, from the viewpoint of the deep curing properties of exposure, the content of photopolymerization initiator is preferably 60% by weight or less, and more preferably 40% by weight or less, relative to the total content of alkali-soluble resin and (E) radical polymerizable compound of 100% by weight.

[0051] From the viewpoint of improving sensitivity during exposure and increasing the hardness of the colored film, (meth)acrylyl is preferred as the radical polymerizable group possessed by (E) radical polymerizable compounds. Here, "(meth)acrylyl" refers to both methacrylyl and acrylyl.

[0052] From the perspective of improving exposure sensitivity, the content of (E) radical polymerizable compound is preferably 5% by weight or more, and more preferably 15% by weight or more, relative to the total content of the alkali-soluble resin and (E) radical polymerizable compound. On the other hand, from the perspective of solderability during the curing process, the content of (E) radical polymerizable compound is preferably 80% by weight or less, and more preferably 60% by weight or less, relative to the total content of the alkali-soluble resin and (E) radical polymerizable compound.

[0053] By using a photoacid generator as a (D) photosensitizer, the alkaline solubility of the exposed part can be relatively improved, thus giving it positive photosensitivity.

[0054] As a photoacid generator, a quinone diazide compound is preferred. More preferably, it is an esterification of a compound with phenolic hydroxyl groups and quinone diazidesulfonyl chloride. To improve alkali solubility, a portion of the phenolic hydroxyl group may be intentionally left unesterified.

[0055] From the viewpoint of pattern processability, the content of quinone diazide compound relative to the total amount of the above-mentioned alkali-soluble resin is preferably 1 to 50 by weight.

[0056] The coloring resin composition of the present invention preferably contains a polymeric dispersant.

[0057] Polymer dispersants refer to polymer chains or groups that possess both pigment-affinity groups that chemically bond or adsorb onto the pigment surface and solvent-affinity properties. In the following wet media dispersion treatments, polymer dispersants achieve the following effects: they improve the wettability of pigments to the dispersion medium, promote pigment depolymerization, stabilize particle size and viscosity through steric hindrance and / or electrostatic repulsion, and thereby inhibit color separation of the coloring resin composition during storage or coating.

[0058] Examples of polymeric dispersants include polyester-based polymeric dispersants, acrylic polymeric dispersants, polyurethane-based polymeric dispersants, polyallylamine polymeric dispersants, carbodiimide dispersants, and polyamide polymeric dispersants. Among these, acrylic polymeric dispersants and polyamide polymeric dispersants are more preferred. As a polyamide polymeric dispersant, it is preferable to have a pectinate structure with several side chains containing polyester chains. More specifically, it is preferable to be a compound in which the main chain has a structure such as polyalkylimide having multiple nitrogen atoms, and has several side chains of polyester chains bonded by amide through the nitrogen atoms. Examples of polyamide dispersants that can be used for this type of serrated structure include: "DISPERBYK" (registered trademark) 2200 (manufactured by BYK-Chemie), "SOLSPERSE" (registered trademark) 11200, 28000 (both manufactured by Lubrizol Co., Ltd.), etc.

[0059] Polymer dispersants are classified as follows: dispersants with an amine value of 1 mgKOH / g or higher and an acid value of less than 1 mgKOH / g; dispersants with an acid value of 1 mgKOH / g or higher and an amine value of less than 1 mgKOH / g; dispersants with an amine value of 1 mgKOH / g or higher and an acid value of 1 mgKOH / g or higher; and dispersants with an amine value of less than 1 mgKOH / g and an acid value of less than 1 mgKOH / g. These may also contain two or more of these types. Among these, dispersants with an amine value of 1 mgKOH / g or higher are preferred.

[0060] Examples of high molecular weight dispersants with an amine value of 1 mgKOH / g or higher and an acid value of less than 1 mgKOH / g include: "DISPERBYK" (registered trademark) 102, 160, 161, 162, 2163, 164, 2164, 166, 167, 168, 2000, 2050, 2150, 2155, 9075, 9077; "BYK" (registered trademark) - LPN6919, "DISPERBYK" - LPN21116, "DISPERBYK" - LPN6919, etc. N21234 (all of the above are manufactured by BYK-Chemie); "EFKA" (registered trademark) 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403, 4800 (all of the above are manufactured by BASF); "Ajisper" (registered trademark) PB711 (manufactured by Ajinomoto Fine-Techno); "SOLSPERSE" 13240, 13940, 20000, 71000, 76500 (all of the above are manufactured by Lubrizol), etc.

[0061] Examples of high molecular weight dispersants with an amine value of 1 mgKOH / g or higher and an acid value of 1 mgKOH / g or higher include: "DISPERBYK" 142, 145, 2001, 2010, 2020, 2025, 9076, and Anti-Terra-205 (all manufactured by BYK-Chemie); "SOLSPERSE" 24000 (manufactured by Lubrizol); and "Ajisper" PB821, PB880, and PB881 (all manufactured by Ajinomoto). Fine-Techno (manufactured); "SOLSPERSE" 9000, 11200, 13650, 24000SC, 24000GR, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 39000, 56000 (manufactured by Lubrizol (stock)) etc.

[0062] Regarding the content of the polymeric dispersant in the coloring resin composition of the present invention, from the viewpoint of improving dispersion stability, when the total weight of the coloring material (B) is set to 100 parts by weight, the content of the polymeric dispersant in the coloring resin composition of the present invention is preferably 10 parts by weight or more, and more preferably 20 parts by weight or more. On the other hand, from the viewpoint of improving the heat resistance or adhesion of the colored film, the content of the polymeric dispersant relative to the total amount of the coloring material (B) is preferably 100 parts by weight or less, and more preferably 60 parts by weight or less.

[0063] The coloring resin composition of this invention may also contain a thermal crosslinking agent. By containing a thermal crosslinking agent, the strength of the final coating film can be improved. Examples of thermal crosslinking agents include melamine-based crosslinking agents, etc. Crosslinking agents include zoline-based crosslinking agents, carbodiimide-based crosslinking agents, isocyanate-based crosslinking agents, aziridine-based crosslinking agents, and epoxy-based crosslinking agents. Two or more of these may also be present.

[0064] The coloring resin composition of this invention may also contain a leveling agent. By containing a leveling agent, the coatability or surface smoothness of the colored film can be improved. Examples of leveling agents include: anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; cationic surfactants such as stearamine acetate and lauryl trimethylammonium chloride; amphoteric surfactants such as lauryl dimethylamine oxide and lauryl carboxymethyl hydroxyethyl imidazolium betaine; nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate; silicone-based surfactants with polydimethylsiloxane as the main framework; and fluorinated surfactants. Two or more of these may also be contained. Commercially available surfactants include, for example: BYK-302, BYK-333, BYK-3550, and BYK-392 (all manufactured by BYK-Chemie).

[0065] Regarding the coloring resin composition of the present invention, when the coloring film is formed with an optical density (OD value) of 4, the average light transmittance of the coloring film in the near-infrared region with wavelengths of 920 nm to 960 nm is preferably 90% or more, and more preferably 95% or more. If the average light transmittance in the wavelength range of 920 nm to 960 nm is 90% or more, the infrared intensity obtained by the dielectric coloring film can be further improved, and the sensitivity of the near-infrared sensor or the image illumination of the near-infrared camera can be further improved.

[0066] Regarding the coloring resin composition of the present invention, a coloring film is formed on alkali-free glass with a thickness of 0.7 mm in such a way that the OD value is 1. The transmittance chromaticity (x, y) in the CIE1931 (X, Y, Z) colorimetric system measured from the glass surface is preferably 0.23≦x≦0.36 and 0.24≦y≦0.36, more preferably 0.26≦x≦0.36 and 0.28≦y≦0.36.

[0067] Regarding the light transmittance of the colored film, a coating of colored resin composition can be formed on a transparent substrate. After drying the coating by means of a heating plate, the colored film is obtained by heat treatment by means of a hot air oven. The light transmittance of the transparent substrate is used as a reference and measured using a UV-Vis-NIR spectrophotometer. As described above, the colored film is preferably one in which the crosslinking groups contained in resin (A) of the colored resin composition are crosslinked by heat and / or light and are substantially free of residue. For example, when the colored resin composition contains acrylic resin as resin (A), the heat treatment temperature is preferably 170°C or higher, and the heat treatment time is preferably 30 minutes or higher. The UV-Vis spectrophotometer is preferably UV-3150 (manufactured by Shimadzu Corporation), and the transparent substrate is preferably TEMPAX (manufactured by AGC Techno Glass Corporation), which is a transparent glass substrate. Furthermore, regarding the OD value of the coating or coloring film, an optical density meter (manufactured by 361TVisual;X-Rite) can be used to measure the intensity of incident light and transmitted light of the coating or coloring film, and the OD value of the coating or coloring film can be calculated by the following formula (3). OD value = log 10(I 0 / I)···Equation (3) I0: Incident light intensity I: Intensity of transmitted light.

[0068] As for the optical density (OD value) of the colored film obtained by the coloring resin composition of the present invention, the OD value per 1 μm film thickness is preferably 0.5 or more, and more preferably 0.7 or more. The higher the OD value per unit film thickness, that is, the lower the transmittance in the visible light range, the thinner the film thickness can be to achieve the desired visible light blocking properties.

[0069] Regarding the coloring resin composition of this invention, a coloring film is formed on 0.7 mm thick alkali-free glass with an OD value of 4. The reflectance chromaticity values ​​(a*, b*) obtained from the glass surface using the SCI method in the CIE1976 (L*, a*, b*) colorimetric system are preferably -0.5 ≤ a* ≤ 1.0 and -1.0 ≤ b* ≤ 0.5, more preferably 0.0 ≤ a* ≤ 1.0 and -1.0 ≤ b* ≤ 0.0. Reflectance chromaticity serves as an indicator of the hue of the image projected onto the coloring film. In the SCI method, the closer (a*, b*) is to (0.0, 0.0), the more likely it is to be considered a non-color reflectance hue. On the other hand, regarding the non-lit reflectance hue of liquid crystal display devices or organic electroluminescent (EL) displays, generally speaking, b* in the SCI method is negative, indicating a blue hue. Therefore, the decorative film used in the display device preferably has a negative b* value. The reflectance chromaticity value (L*) in the CIE1976 (L*, a*, b*) color system, obtained by measuring the colored film formed in the same manner on the glass surface using the SCE method, is preferably L*≦3.0, more preferably L*≦2.0. In the SCI method, (L*) represents the diffuse reflectance; the closer it is to (L*)=(0.0), the more it can be described as a jet-black reflectance hue. From a design perspective, a jet-black reflectance hue is preferred.

[0070] The colorimetric values ​​obtained using a colorimeter are significantly affected by the illumination and the geometry of the light source. The geometric conditions of a colorimeter are broadly categorized into 45-degree illumination systems and diffuse illumination systems using an integrating sphere. Diffuse illumination systems are further divided into those including the specular component (SCI) and those excluding the specular component (SCE), depending on how the specular reflection component of the light trap is processed. In SCI, all specular reflection components generated by the sample are integrated. On the other hand, in SCE, the specular reflection component is removed by the light trap located on the wall of the integrating sphere, thus measuring the diffuse reflection component.

[0071] The reflectance chromaticity (L*, a*, b*) of the colored film can be obtained by using a spectrophotometer (CM-2600d; Konica Minolta) calibrated with a white calibration plate (CM-A145; manufactured by Konica Minolta) under the following conditions: standard light source D65 (color temperature 6504 K), viewing angle 2° (CIE1976), atmospheric pressure, and 20°C. The total internal reflection chromaticity (SCI) and diffuse reflectance chromaticity (SCE) of light incident from a transparent substrate are measured.

[0072] A preferred method for manufacturing the coloring resin composition of the present invention is, for example, the following method: using a disperser to disperse a resin solution containing (A) resin, (B) colorant, and (C) organic solvent, a colorant dispersion with a high concentration of colorant is prepared in advance, and then (A) resin, or other components such as photosensitizer as needed, are added and stirred. Filtration may also be performed as needed.

[0073] In this invention, it is preferred to use pigments that have undergone pre-micronization treatment as coloring material (B). Examples of means of micronizing pigments include: salt milling treatment, in which pigments, inorganic salts and organic solvents are mixed and ground; or acidic slurry treatment, in which pigments are temporarily dissolved in strong acids such as sulfuric acid and mixed with unsuitable solvents; etc.

[0074] A preferred method for salt milling is to mix pigments, water-soluble inorganic salts, and organic solvents that do not dissolve the inorganic salts, then immerse the mixture in water, and filter and wash the resulting slurry to remove the inorganic salts. Alternatively, a polymeric dispersant or other resin or pigment derivative can be added along with the pigments, water-soluble inorganic salts, and organic solvents to inhibit the re-agglomeration of pigments after micronization using salt milling.

[0075] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, calcium chloride, barium chloride, and sodium sulfate.

[0076] As an organic solvent, there are no particular limitations as long as it is water-soluble and does not dissolve water-soluble inorganic salts. However, since the temperature rises during salt milling, it becomes an organic solvent that is easily evaporated. Therefore, from a safety perspective, high-boiling-point solvents are preferred. Examples include: 2-methoxyethanol, 2-butoxyethanol, 2-(isopentoxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low molecular weight polypropylene glycol, etc. Two or more of these can also be used.

[0077] Examples of mixing devices include: kneaders, mixing machines, "Trimix" (registered trademark) manufactured by Inoue Manufacturing Co., Ltd. as a planetary mixer, and "Miracle KCK" (registered trademark) manufactured by Asada Iron Works Co., Ltd. as a continuous single-shaft mixing machine.

[0078] Examples of dispersers used to disperse resin solutions containing (A) resin, (B) colorant, and (C) organic solvent include: ball mills, bead mills, sand mills, three-roll mills, and high-speed impact mills. Among these, bead mills are preferred for maximizing dispersion efficiency and achieving micro-dispersion. Examples of bead mills include: coball mills, basket mills, pin mills, and dyno mills. Examples of beads used in bead mills include: titanium dioxide beads, zircon beads, and zircon beads.

[0079] In this invention, dispersion is preferably carried out in multiple stages using a bead mill, and preferably includes the following step: using beads with an average particle size greater than 0.1 mm. After dispersion treatment in a bead mill, the beads are made with an average bead size of 0.1 mm. The following steps involve dispersing the beads using a bead mill. This is achieved by using beads with an average particle size greater than 0.1 mm. The pigment beads are dispersed using a bead mill, which efficiently crushes pigments with larger crystal sizes. Subsequently, beads with an average particle size of 0.1 mm are used. The following micro-beads are dispersed using a bead mill, which reduces the energy applied to the pigment, maintaining its surface activity while achieving micro-dispersion. This inhibits re-aggregation of the pigment in the coloring resin composition, resulting in a more uniform dispersion. In this case, it is preferable that the bead mill is equipped with a separator capable of separating the micro-beads from the dispersion using centrifugal separation. Here, the average bead diameter refers to the average number of bead diameters equivalent to the circumference of the beads. Specifically, the bead diameter can be determined by photographing the beads at 45x magnification using a stereomicroscope, measuring the longest and shortest diameters of 100 randomly selected beads, setting their average as the equivalent circumference diameter, and calculating the average number of beads.

[0080] A colored film can be obtained by forming the coloring resin composition of the present invention into a film. Specifically, the coloring resin composition of the present invention is coated onto a transparent substrate such as glass, plastic, or film. In the case of an organic solvent, the organic solvent is dried, distilled off, and then a hardening reaction is carried out as needed to obtain a colored film. There are no particular limitations on the coating method. Depending on the liquid properties of the substrate and the coloring resin composition, examples include: screen printing, offset printing, pad printing, letterpress printing, gravure printing, inkjet printing, gravure coating, roller coating, reverse roller coating, roller blade coating, rod coating, curtain flow coating, die coating, spin coating, air knife coating, and spray coating.

[0081] Secondly, regarding examples of methods for forming colored films using the colored resin composition of the present invention, a negative photosensitive colored resin composition will be used as an example for explanation.

[0082] A photosensitive coloring resin composition is coated onto a substrate to obtain a coated film. Examples of substrates include transparent substrates such as soda glass, alkali-free glass, and quartz glass; silicon wafers, ceramic substrates, and gallium arsenide substrates. Examples of coating methods include spin coating using a spin coater, spray coating, inkjet coating, die coating, and roll coating. The film thickness can be appropriately selected depending on the coating method. Generally, the film thickness after drying is set to 1~150 μm.

[0083] The obtained coated film is dried to obtain a dried film. Examples of drying methods include: heat drying, air drying, reduced pressure drying, and infrared irradiation. Examples of heat drying devices include: ovens and heating plates. The preferred drying temperature is 50~150℃, and the preferred drying time is 1 minute to several hours.

[0084] A mask with the desired pattern is used to irradiate the obtained dried film with photochemical rays to obtain an exposed film. Examples of photochemical rays that can be irradiated include ultraviolet light, visible light, electron beams, and X-rays. Preferably, the coloring resin composition of the present invention is irradiated with i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp.

[0085] The obtained exposed film is developed using an alkaline developer, thereby removing the unexposed areas and obtaining a pattern. Examples of alkaline compounds used in alkaline developers include: inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilate, and ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), and quaternary ammonium salts such as choline; alcohol amines such as triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, and diethylaminoethanol; pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonane. Organic bases such as cyclic amines and porphyrins.

[0086] The concentration of alkaline compounds in alkaline developing solutions is typically 0.01–50% by weight, preferably 0.02–3% by weight. Furthermore, to improve the shape of the developed pattern, 0.1–5% by weight of nonionic surfactants or other surfactants may be added. Moreover, when the developing solution is an alkaline aqueous solution, water-soluble organic solvents such as ethanol, γ-butyrolactone, dimethylformamide, and N-methyl-2-pyrrolidone may be added.

[0087] Examples of developing methods include immersion, spraying, and liquid coating. The obtained pattern can also be rinsed with pure water.

[0088] Patterned colored films can be obtained by heat-treating (post-baking) the obtained pattern. The heat treatment can be performed under any conditions, including in air, nitrogen atmosphere, or vacuum. The preferred heating temperature is 150–300°C, and the preferred heating time is 0.25–5 hours. The heating temperature can be continuously changed or changed in stages.

[0089] The colored resin composition and colored film of this invention have high light-blocking properties in the visible light region and high transmittance in the near-infrared region. Moreover, the reflected and transmitted tones are non-color. Therefore, they are suitable for colored films on decorative substrates in display terminals such as smartphones or personal computers (PCs), colored films for near-infrared sensors and near-infrared cameras used for driver monitoring or gesture sensors in automotive displays or instrument panels, decorative films and resin molded articles for LiDAR sensors, colored films for icons in automotive displays or instrument panels, light-blocking images such as black matrices of color filters in liquid crystal display devices, and colored spacers inside organic EL displays.

[0090] The decorative substrate of this invention refers to a substrate comprising a support for a coloring film and the coloring film of this invention, wherein decoration (including the case of a single color) is achieved by means of the coloring film of this invention. Examples of decorative substrates include: cover glass substrates for smartphones or tablet PCs, automotive displays, etc., or lens substrates for concealing near-infrared cameras or near-infrared sensors. [Example]

[0091] The present invention will be described in detail below with specific examples, but the present invention is not limited to the examples given herein.

[0092] <Evaluation Methods> [Pigment crystallite size] The coloring resin composition was coated onto a 0.7 mm thick alkali-free glass substrate (AN100) using a rotator (1H-DS) manufactured by Mikasa Corporation. The coated film was then heated and dried on a 100°C heating plate for 2 minutes. The dried film was then baked in a hot air oven at 230°C for 30 minutes to obtain the colored film. The colored film was then shaved off the glass plate and placed into an aluminum standard sample holder. The X-ray diffraction spectrum was measured using a DS ADVANCE (trade name) X-ray diffraction apparatus manufactured by Bruker AXS Corporation, with the X-ray source being CuKα rays, via wide-angle X-ray diffraction. The measurement conditions were: output 40 kV / 40 mA, slit system: Div. Slit: 0.3°, measurement step (2θ): 0.0171°, and measurement time: 0.5 seconds / step. The diffraction angle and half-width at half-maximum of the obtained main peak were measured, and the crystal size was calculated using the Scherrer formula expressed in the above formula (1).

[0093] The methylimine-based pigment Bk-1 described in Manufacturing Example 1 exhibited the strongest main peak at a diffraction angle of 2θ = 26.25° or higher and 26.45° or lower. The bisbenzofuranone-based pigment Bk-2 described in Manufacturing Example 2 exhibited the strongest main peak at a diffraction angle of 2θ = 7.80° or higher and 8.00° or lower.

[0094] [Light-blocking properties] For the colored film, the OD value per 1 μm of film thickness was calculated using an X-Rite 361TVisual optical density meter.

[0095] [Visible light transmittance chromaticity and near-infrared transmittance] For the colored film formed with an OD value adjusted to 1.0, the transmittance from wavelengths of 380 nm to 780 nm was measured using a UV-3150 UV-Vis spectrophotometer manufactured by Shimadzu Corporation, and the transmittance chromaticity (x, y) was determined. For the colored film formed with an OD value adjusted to 4.0, the transmittance from wavelengths of 920 nm to 960 nm was measured in the same manner, and the average transmittance was determined. A higher average transmittance indicates better light transmission in the near-infrared region. Furthermore, the transmittance values ​​shown in the table represent only the values ​​for the colored film; the substrate was used as a reference for transmittance measurement.

[0096] [Near-infrared camera image] For the color coating, the Freemo infrared camera module manufactured by Alpha Technology was placed on the back of the color coating, and the obtained camera images were evaluated based on the following criteria. A: A clear image can be confirmed. B: Although an image can be confirmed, the outline is unclear. C: Image not confirmed.

[0097] [Reflectance Chromaticity] For the colored film formed after adjusting the OD value to 4.0, a spectrophotometer (CM-2600d; Konica Minolta) calibrated with a white calibration plate (CM-A145; manufactured by Konica Minolta) was used to measure the total internal reflection chromaticity (SCI) and diffuse reflectance chromaticity (SCE) of light incident from a transparent substrate under the following conditions: standard light source D65 (color temperature 6504 K), viewing angle 2° (CIE1976), atmospheric pressure, and 20°C. The reflectance chromaticity (L*, a*, b*) was evaluated.

[0098] (Synthesis Example 1: Synthesis of Acrylic Resin (P-1)) A copolymer of methyl methacrylate / methacrylic acid / styrene (weight ratio 30 / 40 / 30) was synthesized using the method described in Example 1 of Japanese Patent No. 3120476. For 100 parts by weight of the obtained copolymer, 40 parts by weight of glycidyl methacrylate were added, and the mixture was reprecipitated with purified water, filtered, and dried to obtain an acrylic resin (P-1) with a weight average molecular weight of 15,000 and an acid value of 110 mgKOH / g. Furthermore, the acid value of the acrylic resin was defined as the amount of potassium hydroxide (mg) required to neutralize 1 g of the acrylic resin (unit: mgKOH / g). The weight average molecular weight was determined using gel permeation chromatography (GPC) "HLC-8220GPC" (a testing apparatus manufactured by Tosho Corporation), with the carrier as tetrahydrofuran and converted to polystyrene.

[0099] (Manufacturing Example 1: Manufacturing of Methylimide-based Pigment Bk-1) Chromofine Black A1103, manufactured by Dai Nippon Seika Kogyo Co., Ltd. (a methylimino pigment), 2400 g of sodium chloride, and 400 g of diethylene glycol were added to a kneader (Moriyama Seisakusho Co., Ltd., S-type kneader (trade name)) and kneaded at 70°C for 8 hours. Next, the mixture was added to approximately 10 L of warm water and heated to 40°C while being stirred by a high-speed mixer for 1 hour to form a slurry. After that, it was filtered and washed with water to remove sodium chloride and diethylene glycol, and then vacuum dried at 80°C for 24 hours to obtain methylimino pigment Bk-1.

[0100] (Manufacturing Example 2: Manufacturing of bisbenzofuran pigment Bk-2) Irgaphor Black S0100CF, manufactured by BASF (co.g.), a bisbenzofuran pigment, along with 2400 g of sodium chloride and 400 g of diethylene glycol, were added to a kneader (Moriyama Seisakusho, S-type kneader, trade name) and kneaded at 70°C for 8 hours. Next, the mixture was placed in approximately 10 L of warm water and heated to 40°C while being stirred in a high-speed mixer for 1 hour to form a slurry. Afterward, the slurry was filtered, washed with water to remove sodium chloride and diethylene glycol, and then vacuum-dried at 80°C for 24 hours to obtain the bisbenzofuran pigment Bk-2.

[0101] (Manufacturing Example 3: Manufacturing of Blue Pigment PB15:6-1) 200 g of "LIONOL BLUE ES" (PB15:6) manufactured by Toyocolor (Co., Ltd.), 2400 g of sodium chloride, and 400 g of diethylene glycol were added to a kneader (Moriyama Seisakusho (Co., Ltd., S-type kneader (trade name)) and kneaded at 70°C for 8 hours. Next, the mixture was added to approximately 10 L of warm water and heated to 40°C while being stirred by a high-speed mixer for 1 hour to form a slurry. Afterward, the slurry was filtered and washed with water to remove sodium chloride and diethylene glycol, and then vacuum dried at 80°C for 24 hours to obtain the blue pigment PB15:6-1.

[0102] (Manufacturing Example 4: Manufacturing of Red Pigment PR177-1) Using "Cromophtal Red A3B" (PR177) manufactured by BASF (stock) instead of "LIONOL BLUE ES" (PB15:6) manufactured by Toyocolor (stock), the red pigment PR177-1 was obtained in the same manner as in manufacturing example 3.

[0103] (Manufacturing Example 5: Manufacturing of Yellow Pigment PY150-1) Lanxess (stock) manufactured "E-4GN" (PY150) was used instead of Toyocolor (stock) manufactured "LIONOL BLUE ES" (PB15:6). Otherwise, yellow pigment PY150-1 was obtained in the same manner as in manufacturing example 3.

[0104] (Manufacturing Example 6: Manufacturing of Colorant Dispersion (D-1)) 120 g of imine-based pigment Bk-1, 171 g of a 35% by weight solution of propylene glycol monomethyl ether acetate (PGMEA) of acrylic resin (P-1) obtained in Synthesis Example 1, 20 g of polyamide-based polymeric dispersant "DISPERBYK" 2200 (BYK-2200) as a polymeric dispersant, and 689 g of PGMEA were added to a tank and stirred for 20 minutes using a homogenizer to obtain a pre-dispersion. The mixture was then added to a tank filled with beads with a diameter of 0.30 mm. The prepared dispersion was fed into an Ultra Apex Mill UAM015 disperser manufactured by Kosei Kogyo Co., Ltd., containing 75% by volume of zirconia beads and equipped with a centrifugal separator. The dispersion was then dispersed at a rotational speed of 12 m / s for 20 minutes. Subsequently, the dispersed liquid was fed into a container filled with beads with a diameter of 0.05 mm. Zirconia beads were dispersed in Ultra Apex Mill UAM015 at a rotation speed of 8 m / s for 90 minutes to obtain a colorant dispersion D-1 with a solid content of 20% by weight and a colorant / (resin + dispersant) (weight ratio) of 60 / 40.

[0105] (Manufacturing Example 7: Manufacturing of Colorant Dispersion (D-2)) 120 g of the imine-based pigment Bk-1, 171 g of a 35% by weight solution of propylene glycol monomethyl ether acetate (PGMEA) of the acrylic resin (P-1) obtained in Synthesis Example 1, 20 g of the polyamide-based polymeric dispersant "DISPERBYK" 2200 (BYK-2200) as a polymeric dispersant, and 689 g of PGMEA were added to a tank and stirred for 20 minutes using a homogenizer to obtain a pre-dispersion. Beads with a diameter of 1.00 mm were used. Zirconia beads were dispersed for 3 hours using a coating shaker (Toyo Seiki Co., Ltd.), and then filtered through a 5 μm filter to obtain a coloring material dispersion D-2 with a solid content of 20% by weight and a coloring material / (resin + polymer dispersant) (weight ratio) of 60 / 40.

[0106] (Manufacturing Example 8: Manufacturing of Colorant Dispersion (D-3)) The bisbenzofuran pigment Bk-2 was used instead of the methylimine pigment Bk-1. Otherwise, the coloring material dispersion D-3 with a solid content of 20% by weight and a coloring material / (resin + dispersant) (weight ratio) of 60 / 40 was obtained in the same manner as in Manufacturing Example 6.

[0107] (Manufacturing Example 9: Manufacturing of Colorant Dispersion (D-4)) The bisbenzofuran pigment Bk-2 was used instead of the methylimine pigment Bk-1. Otherwise, the coloring material dispersion D-4 with a solid content of 20% by weight and a coloring material / (resin + dispersant) (weight ratio) of 60 / 40 was obtained in the same manner as in Manufacturing Example 7.

[0108] (Manufacturing Example 10: Manufacturing of Colorant Dispersion (D-5)) 120 g of the blue pigment PB15:6-1, 171 g of a 35% by weight solution of propylene glycol monomethyl ether acetate (PGMEA) of the acrylic resin (P-1) obtained in Synthesis Example 1, 20 g of the amine polymeric dispersant "BYK LPN-21116" as a polymeric dispersant, and 689 g of PGMEA were added to a tank and stirred for 20 minutes using a homogenizer to obtain a pre-dispersion. The mixture was then added to a container filled with beads with a diameter of 0.50 mm. The prepared dispersion was fed into an Ultra Apex Mill UAM015 disperser manufactured by Kosei Kogyo Co., Ltd., containing 75% by volume of zirconia beads and equipped with a centrifugal separator. The dispersion was then dispersed at a rotational speed of 12 m / s for 20 minutes. Subsequently, the dispersed liquid was fed into a container filled with beads with a diameter of 0.05 mm. Zirconia beads of 75% by volume were dispersed in Ultra Apex Mill UAM015 at a rotation speed of 8 m / s for 90 minutes to obtain a colorant dispersion D-5 with a solid content of 20% by weight and a colorant / (resin + polymeric dispersant) (weight ratio) of 60 / 40.

[0109] (Manufacturing Example 11: Manufacturing of Colorant Dispersion (D-6)) The red pigment PR177-1 was used instead of the blue pigment PB15:6-1. Otherwise, the coloring material dispersion D-6 with a solid content of 20% by weight and a coloring material / (resin + dispersant) (weight ratio) of 60 / 40 was obtained in the same manner as in manufacturing example 10.

[0110] (Manufacturing Example 12: Manufacturing of Colorant Dispersion (D-7)) Yellow pigment PY150-1 was used instead of blue pigment PB15:6-1. Otherwise, a coloring material dispersion D-7 with a solid content of 20% by weight and a coloring material / (resin + dispersant) (weight ratio) of 60 / 40 was obtained in the same manner as in manufacturing example 10.

[0111] (Manufacturing Example 13: Manufacturing of Colorant Dispersion (D-8)) 120 g of imine-based pigment Bk-1, 171 g of a 35% by weight solution of propylene glycol monomethyl ether acetate (PGMEA) of acrylic resin (P-1) obtained in Synthesis Example 1, 20 g of polyamide-based polymeric dispersant "DISPERBYK" 2200 (BYK-2200) as a polymeric dispersant, and 689 g of PGMEA were added to a tank and stirred for 20 minutes using a homogenizer to obtain a pre-dispersion. The mixture was then added to a tank filled with beads with a diameter of 0.30 mm. The prepared dispersion was fed into an Ultra Apex Mill UAM015 disperser manufactured by Kosei Corporation, containing 75% by volume of zirconia beads and equipped with a centrifugal separator. The dispersion was carried out at a rotation speed of 12 m / s for 20 minutes. Subsequently, the dispersed liquid was fed into a container filled with beads with a diameter of 0.10 mm. Zirconia beads of 75% by volume were dispersed in Ultra Apex Mill UAM015 at a rotation speed of 8 m / s for 90 minutes to obtain a colorant dispersion D-8 with a solid content of 20% by weight and a colorant / (resin + dispersant) (weight ratio) of 60 / 40.

[0112] (Manufacturing Example 14: Manufacturing of Colorant Dispersion (D-9)) 120 g of imine-based pigment Bk-1, 171 g of a 35% by weight solution of propylene glycol monomethyl ether acetate (PGMEA) of acrylic resin (P-1) obtained in Synthesis Example 1, 20 g of polyamide-based polymeric dispersant "DISPERBYK" 2200 (BYK-2200) as a polymeric dispersant, and 689 g of PGMEA were added to a tank and stirred for 20 minutes using a homogenizer to obtain a pre-dispersion. The mixture was then added to a tank filled with beads with a diameter of 0.30 mm. The prepared dispersion was fed into an Ultra Apex Mill UAM015 disperser manufactured by Kosei Kogyo Co., Ltd., containing 75% by volume of zirconia beads and equipped with a centrifugal separation separator. The dispersion was then dispersed at a rotation speed of 12 m / s for 20 minutes. Subsequently, the dispersed liquid was fed into a container filled with beads with a diameter of 0.03 mm. Zirconia beads of 75% by volume were dispersed in Ultra Apex Mill UAM015 at a rotation speed of 8 m / s for 90 minutes to obtain a colorant dispersion D-9 with a solid content of 20% by weight and a colorant / (resin + dispersant) (weight ratio) of 60 / 40.

[0113] (Manufacturing Example 15: Manufacturing of Colorant Dispersion (D-10)) The bisbenzofuran pigment Bk-2 was used instead of the methylimine pigment Bk-1. Otherwise, the coloring material dispersion D-10 with a solid content of 20% by weight and a coloring material / (resin + dispersant) (weight ratio) of 60 / 40 was obtained in the same manner as in manufacturing example 14.

[0114] (Manufacturing Example 16: Manufacturing of Colorant Dispersion (D-11)) 120 g of bisbenzofuran pigment Bk-2, 171 g of a 35% by weight solution of propylene glycol monomethyl ether acetate (PGMEA) of acrylic resin (P-1) obtained by Synthesis Example 1, 20 g of polyamide-based polymeric dispersant "DISPERBYK" 2200 (BYK-2200) as a polymeric dispersant, and 689 g of PGMEA were added to a tank and stirred for 20 minutes using a homogenizer to obtain a pre-dispersion. The mixture was then added to a tank filled with beads with a diameter of 0.30 mm. The prepared dispersion was fed into an Ultra Apex Mill UAM015 disperser manufactured by Kosei Kogyo Co., Ltd., containing 75% by volume of zirconia beads and equipped with a centrifugal separator. The dispersion was carried out at a rotation speed of 12 m / s for 20 minutes. Subsequently, the dispersed liquid was fed into a container filled with beads with a diameter of 0.02 mm. Zirconia beads of 75% by volume were dispersed in Ultra Apex Mill UAM015 at a rotation speed of 8 m / s for 90 minutes to obtain a colorant dispersion D-11 with a solid content of 20% by weight and a colorant / (resin + dispersant) (weight ratio) of 60 / 40.

[0115] The composition and dispersion conditions of the coloring material dispersions of Examples 6 to 16 are shown in Table 1.

[0116] [Table 1] Table 1 (A) Resin (B) Coloring material (C) Organic solvents dispersant Dispersion conditions Coloring material dispersion 1 D-1 P-1 Methylimide pigments Bk-1 PGMEA BYK-2200 0.30 mm Beads: 12 m / s × 20 minutes +0.05 mm Beads: 8 m / s × 90 minutes Coloring material dispersion 2 D-2 P-1 Methylimide pigments Bk-1 PGMEA BYK-2200 1.00 mm Beads: Paint shaker × 3 hours Coloring material dispersion 3 D-3 P-1 Dibenzofuranone pigments Bk-2 PGMEA BYK-2200 0.30 mm Beads: 12 m / s × 20 minutes +0.05 mm Beads: 8 m / s × 90 minutes Coloring material dispersion 4 D-4 P-1 Dibenzofuranone pigments Bk-2 PGMEA BYK-2200 1.0 mm Beads: Paint shaker × 3 hours Coloring material dispersion 5 D-5 P-1 PB15:6-1 PGMEA BYK LPN-21116 0.50 mm Beads: 12 m / s × 20 minutes +0.05 mm Beads: 8 m / s × 90 minutes Coloring material dispersion 6 D-6 P-1 PR177-1 PGMEA BYK LPN-21116 0.50 mm Beads: 12 m / s × 20 minutes +0.05 mm Beads: 8 m / s × 90 minutes Coloring material dispersion 7 D-7 P-1 PY150-1 PGMEA BYK LPN-21116 0.50 mm Beads: 12 m / s × 20 minutes +0.05 mm Beads: 8 m / s × 90 minutes Coloring material dispersion 8 D-8 P-1 Methylimide pigments Bk-1 PGMEA BYK-2200 0.30 mm Beads: 12 m / s × 20 minutes +0.10 mm Beads: 8 m / s × 90 minutes Coloring material dispersion 9 D-9 P-1 Methylimide pigments Bk-1 PGMEA BYK-2200 0.30 mm Beads: 12 m / s × 20 minutes +0.03 mm Beads: 8 m / s × 90 minutes Coloring material dispersion 10 D-10 P-1 Dibenzofuranone pigments Bk-2 PGMEA BYK-2200 0.30 mm Beads: 12 m / s × 20 minutes +0.03 mm Beads: 8 m / s × 90 minutes Coloring material dispersion 11 D-11 P-1 Dibenzofuranone pigments Bk-2 PGMEA BYK-2200 0.30 mm Beads: 12 m / s × 20 minutes +0.02 mm Beads: 8 m / s × 90 minutes

[0117] (Example 1) To a mixture of 21.67 g of colorant dispersion (D-1) and 5.42 g of colorant dispersion (D-3), a solution was added consisting of 31.04 g of a 35% by weight solution of acrylic polymer (P-1) PGMEA, 8.33 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a multifunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a bonding modifier, and 0.30 g of a 10% by weight solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, dissolved in 32.90 g of PGMEA. This yielded a colorant resin composition PC-1 with a total solids concentration of 25% by weight and a colorant content of 13 parts by weight relative to 100 parts by weight of total solids.

[0118] The obtained colored resin composition PC-1 was coated onto a 0.7 mm thick alkali-free glass substrate (AN100) using a Mikasa (1H-DS) rotary kiln. The coated film was then heated and dried on a 100°C heating plate for 2 minutes. The dried film was then baked in a hot air oven at 230°C for 30 minutes to obtain the colored film C-1. The results of evaluating the colored film C-1 using the above method are shown in Table 2.

[0119] (Example 2) The colorant dispersion (D-1) was set to 20.31 g, and the colorant dispersion (D-3) was set to 6.77 g. Otherwise, the coloring resin composition PC-2 was obtained in the same manner as in Example 1. The obtained coloring resin composition PC-2 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0120] (Example 3) The colorant dispersion (D-1) and the colorant dispersion (D-3) were both set to 13.54 g. Otherwise, the coloring resin composition PC-3 was obtained in the same manner as in Example 1. The obtained coloring resin composition PC-3 was evaluated in the same way as in Example 1. The results are shown in Table 2. Furthermore, the X-ray diffraction spectrum of the obtained coloring film is shown in Figure 1.

[0121] (Example 4) The colorant dispersion (D-1) was set to 9.48 g, and the colorant dispersion (D-3) was set to 17.60 g. Otherwise, the coloring resin composition PC-4 was obtained in the same manner as in Example 1. The obtained coloring resin composition PC-4 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0122] (Example 5) The colorant dispersion (D-1) was set to 6.77 g, and the colorant dispersion (D-3) was set to 20.31 g. Otherwise, the coloring resin composition PC-5 was obtained in the same manner as in Example 1. The obtained coloring resin composition PC-5 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0123] (Example 6) To a mixture of 41.67 g of colorant dispersion (D-1) and 10.42 g of colorant dispersion (D-3), a solution was added consisting of 20.73 g of a 35% by weight solution of acrylic polymer (P-1) PGMEA, 6.92 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a multifunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a bonding modifier, and 0.30 g of a 10% by weight solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, dissolved in 19.59 g of PGMEA. This yielded a colorant resin composition PC-6 with a total solids concentration of 25% by weight and a colorant content of 25 parts by weight relative to 100 parts by weight of total solids. The obtained colored resin composition PC-6 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0124] (Example 7) The colorant dispersion (D-1) was set to 39.06 g, and the colorant dispersion (D-3) was set to 13.02 g. Otherwise, the coloring resin composition PC-7 was obtained in the same manner as in Example 6. The obtained coloring resin composition PC-7 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0125] (Example 8) The colorant dispersion (D-1) and the colorant dispersion (D-3) were both set to 26.04 g. Otherwise, the coloring resin composition PC-8 was obtained in the same manner as in Example 6. The obtained coloring resin composition PC-8 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0126] (Example 9) The colorant dispersion (D-1) was set to 18.23 g, and the colorant dispersion (D-3) was set to 33.85 g. Otherwise, the coloring resin composition PC-9 was obtained in the same manner as in Example 6. The obtained coloring resin composition PC-9 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0127] (Example 10) The colorant dispersion (D-1) was set to 13.02 g, and the colorant dispersion (D-3) was set to 39.06 g. Otherwise, the coloring resin composition PC-10 was obtained in the same manner as in Example 4. The obtained coloring resin composition PC-10 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0128] (Example 11) To a mixture of 10.00 g of colorant dispersion (D-1) and 2.50 g of colorant dispersion (D-3), a solution was added consisting of 37.02 g of a 35% by weight solution of acrylic polymer (P-1) PGMEA, 9.14 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a multifunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a bonding modifier, and 0.30 g of a 10% by weight solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, dissolved in 40.67 g of PGMEA. This yielded a colorant resin composition PC-11 with a total solids concentration of 25% by weight and a colorant content of 6 parts by weight relative to 100 parts by weight of total solids. The obtained colored resin composition PC-11 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0129] (Example 12) The colorant dispersion (D-1) was set to 9.38 g, and the colorant dispersion (D-3) was set to 3.13 g. Otherwise, the coloring resin composition PC-12 was obtained in the same manner as in Example 11. The obtained coloring resin composition PC-12 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0130] (Example 13) The colorant dispersion (D-1) and the colorant dispersion (D-3) were both set to 6.25 g. Otherwise, the coloring resin composition PC-13 was obtained in the same manner as in Example 11. The obtained coloring resin composition PC-13 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0131] (Example 14) The colorant dispersion (D-1) was set to 4.38 g, and the colorant dispersion (D-3) was set to 8.13 g. Otherwise, the coloring resin composition PC-14 was obtained in the same manner as in Example 11. The obtained coloring resin composition PC-14 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0132] (Example 15) The colorant dispersion (D-1) was set to 3.13 g, and the colorant dispersion (D-3) was set to 9.38 g. Otherwise, the coloring resin composition PC-15 was obtained in the same manner as in Example 11. The obtained coloring resin composition PC-15 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0133] (Example 16) To a mixture of 31.25 g of colorant dispersion (D-1) and 31.25 g of colorant dispersion (D-3), a solution was added consisting of 16.45 g of a 35% by weight solution of acrylic polymer (P-1) PGMEA, 6.34 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a multifunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a bonding modifier, and 0.30 g of a 10% by weight solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, dissolved in 14.04 g of PGMEA. This yielded a colorant resin composition PC-16 with a total solids concentration of 25% by weight and a colorant content of 30 parts by weight relative to 100 parts by weight of total solids. The obtained colored resin composition PC-16 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0134] (Example 17) To a mixture of 36.46 g of colorant dispersion (D-1) and 36.46 g of colorant dispersion (D-3), a solution was obtained by dissolving 12.16 g of a 35% by weight solution of acrylic polymer (P-1) PGMEA, 5.75 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a multifunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a bonding modifier, and 0.30 g of a 10% by weight solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant in 8.49 g of PGMEA. A colorant resin composition PC-17 with a total solids concentration of 25% by weight and a colorant content of 35 parts by weight relative to 100 parts by weight of total solids was obtained. The obtained colored resin composition PC-17 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0135] (Example 18) To a mixture of 40.63 g of colorant dispersion (D-1) and 40.63 g of colorant dispersion (D-3), a solution was obtained by dissolving 8.73 g of a 35% by weight solution of acrylic polymer (P-1) PGMEA, 5.29 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a multifunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a bonding modifier, and 0.30 g of a 10% by weight solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant in 4.05 g of PGMEA. A colorant resin composition PC-18 with a total solids concentration of 25% by weight and a colorant content of 35 parts by weight relative to 100 parts by weight of total solids was obtained. The obtained colored resin composition PC-18 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0136] (Example 19) The coloring resin composition PC-19 was obtained in the same manner as in Example 3, except that coloring material dispersion (D-2) was used instead of coloring material dispersion (D-1). The obtained coloring resin composition PC-19 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0137] (Example 20) The coloring resin composition PC-20 was obtained in the same manner as in Example 3, except that coloring material dispersion (D-4) was used instead of coloring material dispersion (D-3). The obtained coloring resin composition PC-20 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0138] (Example 21) To a mixture of 12.19 g of colorant dispersion (D-1), 12.19 g of colorant dispersion (D-3), and 2.71 g of colorant dispersion (D-5), add 31.02 g of a 35% by weight solution of PGMEA in acrylic polymer (P-1), 8.32 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a multifunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a bonding modifier, and 0.30 g of a 10% by weight solution of PGMEA in the silicone-based surfactant "BYK" 333 (manufactured by BYK-Chemie Co., Ltd.) dissolved in 32.90 mL of water. The solution obtained from g of PGMEA yielded a coloring resin composition PC-21 with a total solids concentration of 25% by weight and a coloring material content of 13 parts by weight relative to 100 parts by weight of total solids. The obtained coloring resin composition PC-21 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0139] (Example 22) To a mixture of 23.44 g of colorant dispersion (D-1), 23.44 g of colorant dispersion (D-3), and 5.21 g of colorant dispersion (D-5), add 20.73 g of a 35% by weight solution of acrylic polymer (P-1) PGMEA, 6.92 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a multifunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a adhesion modifier, and 0.30 g of a 10% by weight solution of PGMEA of silicone-based surfactant "BYK" 333 (manufactured by BYK-Chemie Co., Ltd.) dissolved in 19.59 g of water. The solution obtained from g of PGMEA yielded a coloring resin composition PC-22 with a total solids concentration of 25% by weight and a coloring material content of 25 parts by weight relative to 100 parts by weight of total solids. The obtained coloring resin composition PC-22 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0140] (Example 23) The coloring resin composition PC-23 was obtained in the same manner as in Example 21, except that coloring material dispersion (D-6) was used instead of coloring material dispersion (D-5). The obtained coloring resin composition PC-23 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0141] (Example 24) The coloring resin composition PC-24 was obtained in the same manner as in Example 21, except that coloring material dispersion (D-7) was used instead of coloring material dispersion (D-5). The obtained coloring resin composition PC-24 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0142] (Example 25) The coloring resin composition PC-25 was obtained in the same manner as in Example 18, except that coloring material dispersion (D-8) was used instead of coloring material dispersion (D-1). The obtained coloring resin composition PC-25 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0143] (Example 26) The coloring resin composition PC-26 was obtained in the same manner as in Example 18, except that coloring material dispersion (D-10) was used instead of coloring material dispersion (D-3). The obtained coloring resin composition PC-26 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0144] (Example 27) The coloring resin composition PC-27 was obtained in the same manner as in Example 18, except that coloring material dispersion (D-9) was used instead of coloring material dispersion (D-1). The obtained coloring resin composition PC-27 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0145] (Example 28) The coloring resin composition PC-28 was obtained in the same manner as in Example 18, except that coloring material dispersion (D-11) was used instead of coloring material dispersion (D-3). The obtained coloring resin composition PC-28 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0146] (Comparative Example 1) To a mixture of 41.67 g of colorant dispersion (D-1) and 41.67 g of colorant dispersion (D-3), a solution was added consisting of 7.88 g of a 35% by weight solution of acrylic polymer (P-1) PGMEA, 5.17 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a multifunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a bonding modifier, and 0.30 g of a 10% by weight solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant, dissolved in 2.94 g of PGMEA. This yielded a colorant resin composition PC-29 with a total solids concentration of 25% by weight and a colorant content of 40 parts by weight relative to 100 parts by weight of total solids. The obtained colored resin composition PC-29 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0147] (Comparative Example 2) The colorant dispersion (D-1) was set to 24.38 g, and the colorant dispersion (D-3) was set to 2.71 g. Otherwise, the coloring resin composition PC-30 was obtained in the same manner as in Example 1. The obtained coloring resin composition PC-30 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0148] (Comparative Example 3) The colorant dispersion (D-1) was set to 2.71 g, and the colorant dispersion (D-3) was set to 24.38 g. Otherwise, the coloring resin composition PC-31 was obtained in the same manner as in Example 1. The obtained coloring resin composition PC-31 was evaluated in the same way as in Example 1. The results are shown in Table 2.

[0149] [Table 2-1] Table 2 Coloring resin composition Coloring resin composition (A) resin Coloring material dispersion Coloring material (C) D-1 D-2 D-3 D-4 D-5 D-6 D-7 D-8 D-9 D-10 D-11 Content ※ 1 organic solvents Example 1 PC-1 P-1 80wt% 20wt% 13 parts by weight PGMEA Example 2 PC-2 P-1 75wt% 25wt% 13 parts by weight PGMEA Example 3 PC-3 P-1 50wt% 50wt% 13 parts by weight PGMEA Example 4 PC-4 P-1 35wt% 65wt% 13 parts by weight PGMEA Example 5 PC-5 P-1 25wt% 75wt% 13 parts by weight PGMEA Example 6 PC-6 P-1 80wt% 20wt% 25 portions by weight PGMEA Example 7 PC-7 P-1 75wt% 25wt% 25 portions by weight PGMEA Example 8 PC-8 P-1 50wt% 50wt% 25 portions by weight PGMEA Example 9 PC-9 P-1 35wt% 65wt% 25 portions by weight PGMEA Example 10 PC-10 P-1 25wt% 75wt% 25 portions by weight PGMEA Example 11 PC-11 P-1 80wt% 20wt% 6 parts by weight PGMEA Example 12 PC-12 P-1 75wt% 25wt% 6 parts by weight PGMEA Example 13 PC-13 P-1 50wt% 50wt% 6 parts by weight PGMEA Example 14 PC-14 P-1 35wt% 65wt% 6 parts by weight PGMEA Example 15 PC-15 P-1 25wt% 75wt% 6 parts by weight PGMEA Example 16 PC-16 P-1 50wt% 50wt% 30 portions by weight PGMEA Example 17 PC-17 P-1 50wt% 50wt% 35 parts by weight PGMEA Example 18 PC-18 P-1 50wt% 50wt% 39 servings by weight PGMEA Example 19 PC-19 P-1 50wt% 50wt% 13 parts by weight PGMEA Example 20 PC-20 P-1 50wt% 50wt% 13 parts by weight PGMEA Example 21 PC-21 P-1 45wt% 45wt% 10wt% 13 parts by weight PGMEA Example 22 PC-22 P-1 45wt% 45wt% 10wt% 25 portions by weight PGMEA Example 23 PC-23 P-1 45wt% 45wt% 10wt% 13 parts by weight PGMEA Example 24 PC-24 P-1 45wt% 45wt% 10wt% 13 parts by weight PGMEA Example 25 PC-25 P-1 50wt% 50wt% 39 servings by weight PGMEA Example 26 PC-26 P-1 50wt% 50wt% 39 servings by weight PGMEA Example 27 PC-27 P-1 50wt% 50wt% 39 servings by weight PGMEA Example 28 PC-28 P-1 50wt% 50wt% 39 servings by weight PGMEA Comparative Example 1 PC-29 P-1 50wt% 50wt% 40 portions by weight PGMEA Comparative Example 2 PC-30 P-1 90wt% 10wt% 13 parts by weight PGMEA Comparative Example 3 PC-31 P-1 10wt% 90wt% 13 parts by weight PGMEA ※1: Parts by weight relative to the total solid components of 100 parts by weight

[0150] [Table 2-2] Table 2 (continued) Evaluation results of the colored film X-ray diffraction spectrum of imine-based pigments X-ray diffraction spectra of bisbenzofuranone pigments |α-β|(nm) diffraction angle of the main peak 2θ (°) Half the height and width of the main peak (°) Crystallite size α (nm) diffraction angle of the main peak 2θ (°) Half the height and width of the main peak (°) Crystallite size β (nm) Example 1 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 2 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 3 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 4 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 5 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 6 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 7 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 8 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 9 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 10 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 11 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 12 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 13 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 14 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 15 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 16 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 17 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 18 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 19 26.34 0.278 33.2 7.90 0.424 19.7 13.5 Example 20 26.35 0.529 15.9 7.96 0.307 28.7 12.8 Example 21 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 22 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 23 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 24 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Example 25 26.35 0.484 17.5 7.90 0.424 19.7 2.2 Example 26 26.35 0.529 15.9 7.90 0.479 17.3 1.4 Example 27 26.35 0.741 11.2 7.90 0.424 19.7 8.5 Example 28 26.35 0.529 15.9 7.90 0.785 10.3 5.6 Comparative Example 1 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Comparative Example 2 26.35 0.529 15.9 7.90 0.424 19.7 3.8 Comparative Example 3 26.35 0.529 15.9 7.90 0.424 19.7 3.8

[0151] [Table 2-3] Table 2 (continued) Evaluation results of the colored film Light blocking OD value / um Near-infrared light transmittance (OD=4) Infrared camera Projector Image Reflectance Chromaticity SCI (OD=4) Reflection chromaticity SCE(OD=4) Transmitted chromaticity (OD=1) L* a* b* L* a* b* x y Example 1 0.53 95.5% A 25.35 0.61 -0.29 1.31 0.91 0.71 0.27 0.30 Example 2 0.54 95.6% A 25.30 0.57 -0.32 1.35 0.86 0.68 0.28 0.31 Example 3 0.52 95.5% A 25.22 0.46 -0.38 1.44 0.50 0.64 0.31 0.34 Example 4 0.53 95.7% A 25.19 0.45 -0.39 1.59 0.44 0.62 0.32 0.34 Example 5 0.54 96.2% A 25.14 0.36 -0.44 1.59 0.32 0.53 0.34 0.35 Example 6 1.02 95.2% A 25.54 0.83 -0.02 1.33 0.61 0.63 0.26 0.30 Example 7 1.04 95.4% A 25.52 0.82 -0.06 1.34 0.59 0.61 0.27 0.31 Example 8 0.99 95.3% A 25.43 0.66 -0.19 1.35 0.48 0.54 0.31 0.33 Example 9 0.99 95.4% A 25.40 0.59 -0.22 1.41 0.34 0.51 0.32 0.33 Example 10 0.90 95.6% A 25.37 0.54 -0.28 1.44 0.28 0.48 0.35 0.35 Example 11 0.20 96.9% A 25.22 0.34 -0.47 1.24 0.55 0.56 0.29 0.32 Example 12 0.19 97.2% A 25.18 0.31 -0.48 1.21 0.56 0.56 0.30 0.33 Example 13 0.21 95.6% A 25.11 0.33 -0.51 1.39 0.54 0.47 0.32 0.34 Example 14 0.21 96.2% A 25.11 0.29 -0.52 1.41 0.55 0.42 0.33 0.34 Example 15 0.21 95.5% A 25.13 0.27 -0.55 1.06 0.37 0.41 0.35 0.36 Example 16 1.25 94.8% A 25.64 0.78 -0.08 0.97 0.53 0.27 0.31 0.33 Example 17 1.48 94.7% A 25.91 0.96 0.07 1.02 0.56 0.27 0.31 0.33 Example 18 1.72 94.1% A 25.98 0.99 0.11 1.04 0.59 0.31 0.31 0.33 Example 19 0.51 89.9% B 25.55 0.57 -0.34 3.20 1.02 0.91 0.30 0.35 Example 20 0.52 89.7% B 25.49 0.59 -0.31 3.33 1.12 0.71 0.29 0.33 Example 21 0.47 95.6% A 25.01 0.29 -0.57 1.26 0.29 0.33 0.28 0.33 Example 22 0.82 95.4% A 25.35 0.69 -0.33 0.52 0.32 0.29 0.27 0.33 Example 23 0.46 95.7% A 25.07 0.51 -0.34 1.27 0.33 0.21 0.34 0.34 Example 24 0.44 95.6% A 25.03 0.41 -0.11 1.31 0.19 0.26 0.32 0.36 Example 25 1.66 93.9% A 25.97 0.98 0.09 1.07 0.65 0.35 0.31 0.33 Example 26 1.61 94.3% A 25.98 0.99 0.12 0.98 0.56 0.30 0.31 0.33 Example 27 1.81 94.2% A 25.97 0.97 0.10 0.87 0.53 0.29 0.31 0.33 Example 28 1.76 94.8% A 25.99 0.98 0.11 0.79 0.51 0.28 0.31 0.33 Comparative Example 1 1.68 94.5% A 26.02 1.13 0.20 0.99 0.81 0.28 0.31 0.33 Comparative Example 2 0.51 95.2% A 25.38 0.64 -0.23 1.65 1.15 0.88 0.21 0.23 Comparative Example 3 0.50 96.2% A 25.11 0.27 -0.48 0.61 0.26 0.16 0.37 0.37

[0152] It is known that the coloring resin composition of the embodiment exhibits high visible light opacity and near-infrared transmittance at a film thickness with an OD value of 4.0, resulting in good reflectance. Furthermore, it is known that the transmittance is also good at a film thickness with an OD value of 1.0. On the other hand, coloring resin compositions with a higher proportion of coloring material in the total solids composition result in a higher a* value for reflectance, leading to a reddish hue in the image projected onto the colored film. Conversely, coloring resin compositions with a higher proportion of imine-based pigments in the total coloring material result in higher x and y transmittance values, leading to a yellowish hue in the transmitted color of the colored film. Finally, coloring resin compositions with a higher proportion of bisbenzofuranone-based pigments in the total coloring material result in lower x and y transmittance values, leading to a bluish hue in the transmitted color of the colored film. (Industrial applicability)

[0153] The coloring resin composition of the present invention is suitable as a black decorative ink for forming a light-shielding film for concealing sensor wiring and / or a light-shielding film for concealing near-infrared cameras and / or a light-shielding film for blackout mode icons.

Claims

1. A coloring resin composition comprising (A) a resin and (B) a coloring material, wherein at least a methylimine pigment and a bisbenzofuranone pigment are contained as the (B) coloring material, wherein when the weight of all coloring materials is set to 100 parts by weight, the content of the methylimine pigment is 25 to 80 parts by weight, the content of the bisbenzofuranone pigment is 20 to 75 parts by weight, and the content of the (B) coloring material is 1 to 39 parts by weight relative to the total content of the solid components of 100 parts by weight.

2. The coloring resin composition as claimed in claim 1, wherein, The crystallite size of the above-mentioned methylimine pigments, determined by the following method, is 10 nm or more and 25 nm or less. <Method for determining crystallite size> A film is obtained by coating, drying, and heating the coloring resin composition on a glass substrate. The obtained film is then cut off and placed into an aluminum standard sample holder. For this sample, an X-ray diffraction device is used, with the X-ray source set to CuKα rays, and the X-ray diffraction spectrum is determined by wide-angle X-ray diffraction. Regarding the measurement conditions, the output is 40 kV / 40 mA, the slit system is Div. Slit: 0.3°, the measurement step (2θ) is 0.0171°, and the measurement time is 0.5 seconds / step. The diffraction angle and half-width at half-maximum of the main peak from the pigment are measured and calculated using the Scherrer formula.

3. The coloring resin composition as claimed in claim 2, wherein, The crystallite size of the above-mentioned bisbenzofuranone pigments, determined by the above-mentioned method for measuring crystallite size, is 10 nm or more and 25 nm or less.

4. The coloring resin composition as claimed in claim 2, wherein, When the crystallite size of the above-mentioned imine-based pigment, determined by the above-mentioned method for measuring crystallite size, is set as α (nm), and the crystallite size of the above-mentioned bisbenzofuranone-based pigment is set as β (nm), the value is 3.0≦|α-β|≦10.

0.

5. The coloring resin composition of claim 1 or 2, which contains an alkali-soluble resin as the above-mentioned (A) resin, and further contains (D) a photosensitizer and (E) a free radical polymerizable compound.

6. The colored resin composition as claimed in claim 1 or 2, wherein, In a film formed on alkali-free glass with an optical density (OD value) of 1 on a thickness of 0.7 mm, the transmittance chromaticity (x, y) is 0.23≦x≦0.36 and 0.24≦y≦0.

36.

7. The colored resin composition as claimed in claim 1 or 2, wherein, In a film formed on alkali-free glass with an optical density (OD value) of 4 on a thickness of 0.7 mm, the chromaticity values ​​(a*, b*) obtained by measuring the reflectance chromaticity from the glass surface by SCI method are -0.5≦a*≦1.0 and -1.0≦b*≦0.

5.

8. A colored film comprising (A) a resin and (B) a coloring material, wherein the (B) coloring material comprises at least an imine pigment and a bisbenzofuranone pigment, wherein when the weight of all the coloring materials is set to 100 parts by weight, the imine pigment content is 25 to 80 parts by weight, the bisbenzofuranone pigment content is 20 to 75 parts by weight, and the content of the (B) coloring material is 1 to 39 parts by weight relative to the total content of the solid components of 100 parts by weight.

9. The colored film as claimed in claim 8, wherein, The crystallite size of the above-mentioned bisbenzofuranone pigments, determined by the following method, is 10 nm or more and 25 nm or less. <Method for determining crystallite size> The colored film is placed in an aluminum standard sample holder. For this sample, an X-ray diffraction device is used, with the X-ray source set to CuKα rays, and the X-ray diffraction spectrum is determined by wide-angle X-ray diffraction. Regarding the measurement conditions, the output is 40 kV / 40 mA, the slit system is Div. Slit: 0.3°, the measurement step (2θ) is 0.0171°, and the measurement time is 0.5 seconds / step. The diffraction angle and half-width at half-maximum of the main peak from the pigment are measured and calculated using the Scherrer formula.

10. The colored film as claimed in claim 9, wherein, The crystallite size of the above-mentioned methylimine pigment, determined by the above-mentioned method for measuring crystallite size, is 10 nm or more and 25 nm or less.

11. The colored film as claimed in claim 9, wherein, When the crystallite size of the above-mentioned imine-based pigment, determined by the above-mentioned method for measuring crystallite size, is set as α (nm), and the crystallite size of the above-mentioned bisbenzofuranone-based pigment is set as β (nm), the value is 3.0≦|α-β|≦10.

0.

12. The colored film as requested in item 8 or 9, wherein, The transmittance chromaticity (x, y) of the above-mentioned colored film is 0.23≦x≦0.36 and 0.24≦y≦0.

36. The above-mentioned transmittance chromaticity (x, y) is obtained by directly incidenting light onto the film surface and converted into transmittance chromaticity (x, y) of the equivalent film thickness with an optical density (OD value) of 1.

13. The colored film as requested in item 8 or 9, wherein, The chromaticity values ​​(a*, b*) of the above-mentioned colored film are 0.0≦a*≦1.0 and -1.0≦b*≦0.

0. The chromaticity values ​​(a*, b*) of the above-mentioned reflectance are obtained by directly incidenting light onto the film surface and converted into the chromaticity values ​​(a*, b*) of the reflectance measured by SCI method when the film thickness has an optical density (OD value) of 4.

14. A decorative substrate comprising a substrate and a coloring film of any one of claims 8 to 13.

Images