Colored resin composition, colored film, and decorative substrate

Abstract

The present invention addresses the problem of providing a colored resin composition capable of forming a colored film that has high visible-light blocking properties and near-infrared transmitting properties as well as excellent reflection color tone and transmission color tone, and the present invention provides, as a means for solving the aforementioned problem, a colored resin composition containing a resin (A) and a colorant (B), wherein the colored resin composition contains at least an azomethine-based pigment and a bisbenzofuranone-based pigment as the colorant (B), the content of the azomethine-based pigment being 25-80 parts by weight and the content of the bisbenzofuranone-based pigment being 20-75 parts by weight when the total colorant weight is 100 parts by weight, and the content of the colorant (B) is 1-39 parts by weight with respect to a total content of 100 parts by weight of solid components.

Description

Colored resin composition, colored film, decorated substrate

[0001] The present invention relates to a colored resin composition, a colored film useful as a near-infrared transmitting light-shielding film, and a decorated substrate.

[0002] In recent years, various biometric authentication methods have been adopted in various information terminals, such as smartphones, to enhance security. In addition to conventional fingerprint authentication, facial authentication and iris authentication have also been studied, and near-infrared sensors and near-infrared cameras are used for facial authentication and iris authentication. In automobiles, infrared laser sensors are used in near-infrared sensors, such as motion sensors for in-car displays, near-infrared cameras, such as driver monitoring cameras, and LiDAR (Light Detection and Ranging) sensors, which serve as driving space sensors. The above-mentioned near-infrared sensors and near-infrared cameras are generally placed in decorative sections in non-display areas of various displays or on the periphery of the housing. However, conventionally, transparent or translucent covers have been used, making the near-infrared sensors and near-infrared cameras visible from the outside, which has led to issues with the design. Therefore, filters and colored films with high near-infrared transmittance and low visible light transmittance for concealing near-infrared sensors and near-infrared cameras have been investigated. From the viewpoint of design, it is preferable that the color of the reflection of this filter or colored film be close to the color of the display or the periphery of the housing when it is not lit, and it is particularly preferable that it be an achromatic black color.

[0003] Furthermore, in decorative parts of non-display areas of in-vehicle displays, self-luminous meters, etc., a blackout display method is sometimes used, in which icons appear to float when the backlight is on and appear to be non-existent when the backlight is off. In order to reduce the brightness of the icons when they are on or to improve the seamless feel when they are off, a colored film with a visible light transmittance of, for example, 10 to 80% may be formed on the icon part. Since achromatic colors are preferred for transmitted light when the backlight is on, the transmitted color tone of the colored film formed for blackout type icons is preferably achromatic.

[0004] Typically, the colored film that conceals a near-infrared camera and the colored film for the icon portion of a blackout system are formed from separate colored resin compositions. However, with the recent trend toward more sophisticated in-car displays, designs are being considered in which both a near-infrared camera and a blackout system icon are installed in a single decorative display frame. In such cases, three types of decorative layers are required: a colored film for concealing the sensor wiring, a colored film for concealing the near-infrared camera, and a colored film for the icon. This has led to issues such as increased costs for the printing process and ink. Therefore, a process for forming these three types of decorative layers from a single colored resin composition has been desired.

[0005] For example, studies have been conducted on a colored resin composition that uses a bisbenzofuranone pigment as a colorant, with the crystallite size of the bisbenzofuranone pigment being within a specific range (see, for example, Patent Document 1), and a composition for an infrared filter that uses one or more near-infrared transmitting black colorant selected from the group consisting of bisbenzofuranone pigments, azomethine pigments, and perylene pigments, and further contains 1 to 30% of a colorant different from the near-infrared transmitting black colorant, based on the total solid content (see, for example, Patent Document 2).

[0006] International Publication No. 2019 / 230684 Japanese Patent Application Laid-Open No. 2018-120248

[0007] However, although the colored film in the technology described in Patent Document 1 has excellent light resistance, high visible light blocking properties, and high near-infrared transmittance, it is insufficient in transmission chromaticity and reflection chromaticity.Furthermore, the infrared transmission filter in the technology described in Patent Document 2 has high visible light blocking properties and little noise derived from visible light components, but transmission chromaticity and reflection chromaticity are not taken into consideration.

[0008] Therefore, an object of the present invention is to provide a colored resin composition that has high visible light blocking properties and near-infrared transmittance, and is capable of forming a colored film having excellent reflected color tone and transmitted color tone.

[0009] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by including a resin and a colorant in a colored resin composition, including specific amounts of an azomethine pigment and a bisbenzofuranone pigment as the colorants, and setting the total content of the colorants within a specific range, and have thus completed the present invention.

[0010] That is, the object of the present invention is achieved mainly by the following constitution: A colored resin composition containing (A) a resin and (B) a colorant, wherein the (B) colorant contains at least an azomethine pigment and a bisbenzofuranone pigment, and when the weight of all the colorants is 100 parts by weight, the content of the azomethine 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 (B) colorant is 1 to 39 parts by weight per 100 parts by weight of the total content of solid components.

[0011] The colored resin composition of the present invention is excellent in light transmittance in the near-infrared region (wavelength 800 to 1000 nm) and light blocking properties in the visible region, and can also provide a colored film having excellent reflected color tones and transmitted color tones. The colored resin composition of the present invention can provide an excellent near-infrared camera image, and can provide a colored film having achromatic reflected color tones and transmitted color tones and excellent design properties.

[0012] 1 is an X-ray diffraction profile of the colored film obtained in Example 3.

[0013] The present invention will be described in further detail below.

[0014] The colored resin composition of the present invention contains (A) a resin and (B) a colorant. The (A) resin acts as a binder in the composition, and the (B) colorant acts to enhance or adjust optical properties, particularly the ability to block and absorb visible light. The colored resin composition of the present invention contains at least an azomethine pigment and a bisbenzofuranone pigment as the (B) colorant, and is characterized in that, when the weight of all colorants is 100 parts by weight, the content of the azomethine pigment is 25 to 80 parts by weight and the content of the bisbenzofuranone pigment is 20 to 75 parts by weight. Note that, in this specification, the ranges indicated by "to" are inclusive. By containing specific amounts of the azomethine pigment and the bisbenzofuranone pigment as the (B) colorant and by controlling the content of all colorants in the total solid components to a specific range, a colored film with neutral reflection chromaticity and transmission chromaticity can be obtained. Furthermore, by dispersing the azomethine pigment and the bisbenzofuranone pigment in a specific crystallite size in the colored resin composition and colored film, it is possible to significantly improve near-infrared transmittance while blocking visible light. This allows for clear near-infrared camera images to be obtained through the colored film. Furthermore, it is possible to obtain a jet-black colored film with excellent designability by suppressing the diffuse reflectance. Furthermore, by setting the difference between the crystallite size of the azomethine pigment and the crystallite size of the bisbenzofuranone pigment within a specific range, it is possible to improve the visible light blocking ability without changing the reflectance. The colored film obtained from the colored resin composition of the present invention has achromatic reflection chromaticity and transmission chromaticity, low diffuse reflectance, and high visible light blocking ability and near-infrared transmittance, and is therefore suitable for use as a light-blocking film for concealing sensor wiring and / or a light-blocking film for concealing near-infrared cameras and / or a light-blocking film for blackout-type icons.

[0015] Examples of the resin (A) include acrylic resins, cardo resins, siloxane resins, polyimide resins, polyimide precursors, polyurethane resins, polyester resins, vinyl chloride-vinyl acetate resins, etc. Two or more of these may be contained. Among these, from the viewpoints of the storage stability of the colored resin composition and the adhesion and reliability of the colored film, acrylic resins, polyurethane resins, and polyester resins are preferred, and acrylic resins are particularly preferred.

[0016] The colored resin composition of the present invention may or may not have photosensitivity. However, by containing an alkali-soluble resin as the (A) resin and further containing a (D) photosensitizer described below, the colored resin composition can be made photosensitive. Here, the alkali-soluble resin refers to a resin having either or both of a hydroxyl group and a carboxyl group as an alkali-soluble group, an acid value of 10 mg KOH / g or more, and a weight-average molecular weight (Mw) of 500 to 150,000. Here, the weight-average molecular weight (Mw) refers to a value obtained by analyzing by gel permeation chromatography using tetrahydrofuran as a carrier and converting using a calibration curve based on standard polystyrene. The acid value of the alkali-soluble resin refers to the number of mg of potassium hydroxide required to neutralize 1 g of the alkali-soluble resin (unit: mg KOH / g).

[0017] Examples of alkali-soluble resins include cardo resins, acrylic resins, novolac resins, polyimide resins, polyimide precursors, polybenzoxazole resins, polybenzoxazole precursors, polyamide resins, and siloxane resins, which have alkali-soluble groups. When the colored resin composition has negative photosensitivity, acrylic resins and polyimide resins are preferred from the viewpoint of pattern processability and coating film reliability, and from the viewpoint of dispersion stability, it is more preferable to contain an acrylic resin. On the other hand, when the colored resin composition has positive photosensitivity, polyimide resins, polyimide precursors, polybenzoxazole resins, polybenzoxazole precursors, and siloxane resins are preferred from the viewpoint of pattern processability, and it is more preferable to contain a polyimide resin or polyimide precursor from the viewpoint of pattern processability.

[0018] The colored resin composition of the present invention contains at least an azomethine pigment and a bisbenzofuranone pigment as the (B) colorant. It is important that the azomethine pigment is contained in an amount of 25 to 80 parts by weight and the bisbenzofuranone pigment in an amount of 20 to 75 parts by weight, based on 100 parts by weight of the (B) colorant. By incorporating specific amounts of the azomethine pigment and the bisbenzofuranone pigment as the (B) colorant and controlling the total colorant content within a specific range, a colored film with neutral reflection chromaticity and transmission chromaticity can be obtained. If the azomethine pigment content is less than 25 parts by weight, the transmission chromaticity of the colored film shifts from achromatic to yellowish, resulting in an undesirable yellowish tint of transmitted light when the backlight is turned on. On the other hand, if the azomethine pigment content is more than 80 parts by weight, the transmission chromaticity of the colored film shifts from achromatic to bluish, resulting in an undesirable bluish tint of transmitted light when the backlight is turned on. If the content of the bisbenzofuranone pigment is less than 20 parts by weight, the transmission chromaticity of the colored film shifts from achromatic to bluish, and the transmitted light when the backlight is turned on undesirably takes on a bluish tinge, whereas if the content of the bisbenzofuranone pigment is more than 75 parts by weight, the transmission chromaticity of the colored film shifts from achromatic to yellowish, and the transmitted light when the backlight is turned on undesirably takes on a yellowish tinge.

[0019] The azomethine pigment used in the present invention is not particularly limited as long as it has an azomethine structure (RR'C=NR" (R and R' each independently represent hydrogen, or an aliphatic or aromatic group which may contain a heteroatom such as nitrogen or oxygen, and R" represents an aliphatic or aromatic group which may contain a heteroatom such as nitrogen or oxygen), and specific examples include those described in JP-A-1-170601 and JP-A-2-34664, such as "Chromofine Black A1103" manufactured by Dainichiseika Color & Chemicals Co., Ltd.

[0020] The bisbenzofuranone pigment used in the present invention is a pigment having a 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 pigment may contain two or more compounds having these structures.

[0021]

[0022] In general formulas (I) to (III), R １ and R ２ R each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ３ and R ４ are each independently R １０ , OR １１ , S.R. １１ , C.O.R. １１ , C.O.R. １１ R １２ , N.R. １１ COR １２ , O.C.O.R. １１ , COOR １１ , SCOR １１ , OCSR １１ , COSR １１ , CSOR １１ , CN, a halogen atom or a hydroxyl group. １０ 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; R １１ and R １２ each independently represents 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 each independently represent an integer of 0 to 4.

[0023] The bisbenzofuranone pigment having a structure represented by any one of the general formulas (I) to (III) is known and can be obtained, for example, by the method described in JP-A No. 2012-515233. It is also commercially available, for example, as "Irgaphor" (registered trademark) Black S0100CF (trade name, manufactured by BASF Corporation).

[0024] The crystallite size of the pigment contained in the colored resin composition and the colored film can be calculated from the half-width of the most intense main peak observed in the X-ray diffraction spectrum when CuKα rays are used as the X-ray source, using the Scherrer formula shown in the following formula (1).

[0025]

[0026] In the above formula (1), K is a constant of 0.9, and λ is 0.15418 [nm]. β is expressed by the following formula (2): θ represents half the value of the diffraction angle 2θ corresponding to the diffraction peak.

[0027]

[0028] In the above formula (2), β ｅ is the half-width of the diffraction peak, β Ｏ is the correction value of the half-width (0.13°). Ｏ is calculated in radians.

[0029] The X-ray diffraction spectrum is measured by wide-angle X-ray diffraction using CuKα radiation as the X-ray source. The X-ray diffraction device used is a DS ADVANCE manufactured by Bruker AXS Co., Ltd. or an equivalent device. The measurement conditions are: output 40 kV / 40 mA, slit system Div. Slit: 0.3°, measurement step (2θ) 0.0171°, and measurement time 0.5 seconds / step.

[0030] The colored resin composition of the present invention is prepared by scraping off a film obtained by applying, drying, and heating the colored resin composition to a glass substrate, and measuring the X-ray diffraction spectrum. The crystallite size of the azomethine pigment is preferably 10 nm to 25 nm, more preferably 10 nm to 20 nm, as determined from the half-width of the main peak. This crystallite size is an indicator of the dispersion state of the pigment in the colored film; the smaller the crystallite size, the more finely dispersed the pigment is in the colored film. Here, when the colored resin composition contains a crosslinkable group in the resin (A), the colored film of the present invention is preferably such that the crosslinkable group is crosslinked by heat and / or light and substantially no crosslinkable group remains. Such a colored film can be obtained by forming a coating film of the colored resin composition on a transparent substrate, drying the coating film using a hot plate or the like, and then heating it using a hot air oven or the like. For example, when the colored resin composition contains an acrylic resin as the resin (A), the heating temperature is preferably 170°C or higher, and the heating time is preferably 30 minutes or longer. 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 manufactured from the composition. When the crystallite size of the azomethine pigment in the colored film is larger than 25 nm, the near-infrared transmittance decreases and the transmitted scattered light increases, which reduces the clarity of the infrared camera image obtained through the colored film, and also reduces the diffuse reflectance (L in SCE) in the reflected color. ＊The value) increases, resulting in a decrease in the jet-blackness of the colored film. To obtain clearer infrared camera images and a jet-black reflection color tone with better design, it is more preferable for the azomethine pigment to have a crystallite size of 20 nm or less. On the other hand, if the crystallite size of the azomethine pigment in the colored film is less than 5 nm, the dispersion stability of the pigment decreases, and there is a possibility that the pigment will re-aggregate, resulting in an increase in transmitted scattered light and a decrease in visible light blocking properties. Similarly to the azomethine pigment, the crystallite size of the bisbenzofuranone pigment in the colored film is also preferably 10 nm or more and 25 nm or less, more preferably 10 nm or more and 20 nm or less. Similarly to the azomethine pigment and the bisbenzofuranone pigment, the crystallite size of other colorants is also preferably small, with the range of 10 nm or more and 25 nm or less being preferred. Furthermore, when the crystallite size of the azomethine pigment is α (nm) and the crystallite size of the bisbenzofuranone pigment is β (nm), by satisfying 3.0≦|α−β|≦10.0, the reflectance (L in SCI) can be ＊ ) can be improved without changing the viscosity. Generally, in order to improve the visible light shielding ability of a colored film, it is effective to increase the content of the coloring material in the total solid components. However, in this case, the reflected color of the colored film becomes reddish, which causes a problem of deteriorating design. However, in a preferred embodiment of the present invention, by setting the difference in crystallite size between the azomethine pigment and the bisbenzofuranone pigment to the above range, it is thought that the packing of the coloring material is improved and the visible light shielding ability is improved. As a means for setting the crystallite size of the pigment in the colored film within the above range, it is preferable to stably and uniformly disperse the pigment in a fine state in the resin without causing it to re-aggregate. More specifically, there are mentioned methods such as using a pigment with a small crystallite size and producing a colored resin composition by the method using a bead mill described below.

[0031] (B) By adding other colorants to the azomethine pigment and bisbenzofuranone pigment as the colorant, within a range that does not impair the effects of the present invention, it becomes possible to adjust the transmitted color tone and reflected color tone of the colored film. In this case, it is preferable to add a colorant with a small crystallite size, similar to the azomethine pigment and bisbenzofuranone pigment. Examples of colorants include commonly used organic pigments, inorganic pigments, dyes, etc. In order to improve the heat resistance, reliability, and light resistance of the colored film, organic pigments and inorganic pigments are preferred.

[0032] Examples of organic pigments include diketopyrrolopyrrole pigments; azo pigments such as azo, disazo, and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine; anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, and violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; isoindoline pigments; isoindolinone pigments; quinophthalone pigments; threne pigments; and metal complex pigments.

[0033] Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, white lead, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, red iron oxide, molybdenum red, molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine, Prussian blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.

[0034] Examples of dyes include azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine dyes, and polymethine dyes.

[0035] Examples of black organic pigments include carbon black, perylene black, and aniline black. Examples of mixed-color organic pigments include pseudo-black pigments obtained by mixing two or more pigments having colors such as red, blue, green, purple, yellow, magenta, and cyan. Examples of black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; and oxides, composite oxides, sulfides, nitrides, and oxynitrides of the above metals.

[0036] Examples of white coloring materials include titanium dioxide, barium carbonate, zirconium oxide, calcium carbonate, barium sulfate, alumina white, and silicon dioxide.

[0037] Two or more of these coloring agents may be contained.

[0038] It is important that the content of the (B) colorant is 1 to 39 parts by weight per 100 parts by weight of the total solid components. Here, the solid components refer to the (A) resin, (B) colorant, and (D) photosensitizer and (E) radically polymerizable compound contained in the resin composition. Furthermore, any other components remaining in the colored film when formed are also considered solid components. By controlling the content of the (B) colorant to 1 part by weight or more per 100 parts by weight of the total solid components, the visible light blocking properties can be improved even with a thinner film. It is more preferable that the content of the (B) colorant be 10 parts by weight or more per 100 parts by weight of the total solid components. On the other hand, by controlling the content of the (B) colorant to 39 parts by weight or less per 100 parts by weight of the total solid components, the reflective chromaticity of the colored film can be adjusted to a more achromatic color. Furthermore, the reflection of incident light at the interface between the colored film and other substrates can be suppressed, thereby further improving near-infrared transmittance. The upper limit of the content of the coloring material (B) relative to 100 parts by weight of the total content of the solid components is preferably 35 parts by weight or less.

[0039] The colored resin composition of the present invention preferably contains (C) an organic solvent, as this can improve coatability. The (C) organic solvent has the effect of uniformly dissolving or dispersing the (A) resin and (B) colorant, etc. Furthermore, the (C) organic solvent is preferably a compound having a boiling point of 110 to 250°C or less at atmospheric pressure. Since the colored resin composition of the present invention is expected to be applied using a printing method such as a spin coater, slit coater, screen printing, inkjet, gravure printing, or bar coater, if the boiling point is less than 110°C, the organic solvent will dry quickly, which can easily cause problems with coating uniformity. On the other hand, if the boiling point exceeds 250°C, the organic solvent will remain in the resulting colored film, which may deteriorate the chemical resistance of the colored film.

[0040] Examples of the organic solvent (C) include ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, and alcohols.

[0041] 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 methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran. 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 referred to as "PGMEA"), dipropylene glycol methyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate.Examples of esters include alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate. Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Examples of aromatic hydrocarbons include toluene and xylene. Examples of amides include N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. Examples of alcohols include butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol. Two or more of these may be contained.

[0042] Among these, acetates are preferably used in order to further stabilize the dispersion of the colorant. The content of acetates is preferably 40 to 100 parts by weight, and more preferably 70 to 100 parts by weight, based on 100 parts by weight of the organic solvent (C).

[0043] When the weight of the colored resin composition of the present invention is taken as 100 parts by weight, the content of (C) the organic solvent is preferably 50 parts by weight or more, more preferably 70 parts by weight or more, from the viewpoint of uniformity of the thickness of the coating film in the coating step, while the content of (C) the organic solvent is preferably 95 parts by weight or less, more preferably 90 parts by weight or less, from the viewpoint of suppressing sedimentation of the pigment.

[0044] The colored resin composition of the present invention can be imparted with photosensitivity by containing an alkali-soluble resin as the resin (A) and further containing a photosensitizer (D). The colored resin composition may have so-called negative photosensitivity, in which the alkali solubility of the exposed areas is reduced by pattern exposure through an exposure mask and the unexposed areas are removed with an alkali developer to form a pattern, or may have so-called positive photosensitivity, in which the alkali solubility of the exposed areas is made higher than that of the unexposed areas by pattern exposure through an exposure mask and the exposed areas are removed with an alkali developer to form a pattern. In the present invention, it is preferable to have negative photosensitivity, since it is easy to form a high-resolution pattern even when the light-shielding property is high.

[0045] By containing a photopolymerization initiator (D) as a photosensitizer and further containing a radical polymerizable compound (E), it is possible to impart negative photosensitivity, in which exposed areas are photocured by a radical polymerization reaction. The radical polymerizable compound (E) is preferably a compound having two or more radical polymerizable groups.

[0046] The photopolymerization initiator refers to a compound that generates radicals by bond cleavage and / or reaction upon exposure to light. By including the photopolymerization initiator, the radical polymerizable compound (E) can be photocured upon exposure to light.

[0047] Examples of photopolymerization initiators include carbazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and α-aminoalkylphenone-based photopolymerization initiators. Two or more of these may be contained. Among these, carbazole-based photopolymerization initiators and oxime ester-based photopolymerization initiators are preferred because they have high sensitivity to a mixed line consisting of i-line (365 nm), h-line (405 nm), and g-line (436 nm) in the exposure step described below.

[0048] From the viewpoint of improving sensitivity to light exposure, the content of the photopolymerization initiator is preferably 1% by weight or more based on the total content of the alkali-soluble resin and the radically polymerizable compound (E).

[0049] On the other hand, from the viewpoint of deep curing properties upon exposure to light, the content of the photopolymerization initiator is preferably 60% by weight or less, and more preferably 40% by weight or less, relative to 100% by weight of the total content of the alkali-soluble resin and the radically polymerizable compound (E).

[0050] The radical polymerizable group of the radical polymerizable compound (E) is preferably a (meth)acrylic group from the viewpoints of improving sensitivity during exposure and improving hardness of the colored film. Here, the term "(meth)acrylic group" includes both a methacrylic group and an acrylic group.

[0051] The content of the radical polymerizable compound (E) is preferably 5% by weight or more, more preferably 15% by weight or more, based on the total content of the alkali-soluble resin and the radical polymerizable compound (E) from the viewpoint of improving sensitivity to light exposure, while the content of the radical polymerizable compound (E) is preferably 80% by weight or less, more preferably 60% by weight or less, based on the total content of the alkali-soluble resin and the radical polymerizable compound (E) from the viewpoint of reflowability in the curing step.

[0052] By incorporating a photoacid generator (D) as a photosensitizer, the alkali solubility of the exposed area can be relatively increased, and positive photosensitivity can be imparted to the composition.

[0053] The photoacid generator is preferably a quinone diazide compound. As the quinone diazide compound, an ester of a compound having a phenolic hydroxyl group with quinone diazide sulfonyl chloride is more preferred. In order to improve alkali solubility, some of the phenolic hydroxyl groups may be intentionally left unesterified.

[0054] From the viewpoint of pattern processability, the content of the quinone diazide compound is preferably 1 to 50% by weight based on the total amount of the alkali-soluble resin.

[0055] The colored resin composition of the present invention preferably further contains a polymer dispersant.

[0056] The polymer dispersant is a compound having both a pigment-affinity group that chemically bonds to or adsorbs to the pigment surface and a polymer chain or group that is solvent-philic. In the wet media dispersion treatment described below, the polymer dispersant improves the wettability of the pigment to the dispersion medium, promotes deagglomeration of the pigment, stabilizes the particle size and viscosity by steric hindrance and / or electrostatic repulsion, and further suppresses color separation during storage or application of the colored resin composition.

[0057] Examples of polymer dispersants include polyester-based polymer dispersants, acrylic-based polymer dispersants, polyurethane-based polymer dispersants, polyallylamine-based polymer dispersants, carbodiimide-based dispersants, and polyamide-based polymer dispersants. Among these, acrylic-based polymer dispersants and polyamide-based polymer dispersants are more preferred. Polyamide-based polymer dispersants are preferably those with a comb-like structure having multiple side chains formed from polyester chains. More specifically, compounds having a structure with multiple nitrogen atoms, such as polyalkyleneimine, in the main chain and multiple polyester chain side chains amide-bonded via the nitrogen atoms are preferred. Examples of polyamide-based dispersants with such comb-like structures include "DISPERBYK" (registered trademark) 2200 (manufactured by BYK-Chemie), and "SOLSPERSE" (registered trademark) 11200 and 28000 (both manufactured by Lubrizol Corporation).

[0058] Polymer dispersants are classified into dispersants having an amine value of 1 mgKOH / g or more and an acid value of less than 1 mgKOH / g, dispersants having an acid value of 1 mgKOH / g or more and an amine value of less than 1 mgKOH / g, dispersants having an amine value of 1 mgKOH / g or more and an acid value of 1 mgKOH / g or more, and dispersants having an amine value less than 1 mgKOH / g and an acid value less than 1 mgKOH / g. Two or more of these may be contained. Among these, dispersants having an amine value of 1 mgKOH / g or more are preferred.

[0059] Examples of polymer dispersants having an amine value of 1 mgKOH / g or more 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, and 9077, "BYK" (registered trademark)-LP N6919, "DISPERBYK"-LP N21116, and "DISPERBYK"-LP N31116. N21234 (all manufactured by BYK-Chemie), "EFKA" (registered trademark) 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403, 4800 (all manufactured by BASF), "Ajisper" (registered trademark) PB711 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), "SOLSPERSE" 13240, 13940, 20000, 71000, 76500 (all manufactured by Lubrizol Corporation).

[0060] Examples of polymer dispersants having an amine value of 1 mgKOH / g or more and an acid value of 1 mgKOH / g or more include "DISPERBYK" 142, 145, 2001, 2010, 2020, 2025, 9076, and Anti-Terra-205 (all manufactured by BYK-Chemie), "SOLSPERSE" 24000 (manufactured by Lubrizol Corporation), and "AJISPER" PB821. , PB880, PB881 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), "SOLSPERSE" 9000, 11200, 13650, 24000SC, 24000GR, 32000, 32500, 32550, 326000, 33000, 34750, 35100, 35200, 37500, 39000, 56000 (manufactured by Lubrizol Corporation), and the like.

[0061] The content of the polymer dispersant in the colored resin composition of the present invention is preferably 10 parts by weight or more, and more preferably 20 parts by weight or more, when the total weight of the colorant (B) is 100 parts by weight, from the viewpoint of improving dispersion stability. On the other hand, the content of the polymer dispersant is preferably 100 parts by weight or less, and more preferably 60 parts by weight or less, based on the total amount of the colorant (B), from the viewpoint of improving the heat resistance and adhesion of the colored film.

[0062] The colored resin composition of the present invention may contain a thermal crosslinking agent. By containing a thermal crosslinking agent, the strength of the coating film obtained as a final product can be improved. Examples of the thermal crosslinking agent include a melamine-based crosslinking agent, an oxazoline-based crosslinking agent, a carbodiimide-based crosslinking agent, an isocyanate-based crosslinking agent, an aziridine-based crosslinking agent, and an epoxy-based crosslinking agent. Two or more of these may be contained.

[0063] The colored resin composition of the present invention may contain a leveling agent. By containing a leveling agent, it is possible to improve the coatability and the surface smoothness of the colored film. Examples of leveling agents include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether triethanolamine sulfate; cationic surfactants such as stearylamine 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 having a polydimethylsiloxane or the like as a main skeleton; and fluorine-based surfactants. Two or more of these may be contained. Examples of commercially available surfactants include "BYK"-302, "BYK"-333, "BYK"-3550, and "BYK"-392 (all manufactured by BYK-Chemie).

[0064] The colored resin composition of the present invention preferably has an average light transmittance of 90% or more, more preferably 95% or more, in the near-infrared region of wavelengths from 920 nm to 960 nm when a colored film is formed so as to have an optical density (OD value) of 4. When the average light transmittance in the wavelength range from 920 nm to 960 nm is 90% or more, the intensity of infrared light obtained through the colored film can be further improved, and the sensitivity of the near-infrared sensor and the illuminance of the near-infrared camera image can be further improved.

[0065] The colored resin composition of the present invention forms a colored film on an alkali-free glass having a thickness of 0.7 mm so that the OD value is 1, and the transmission chromaticity (x, y) in the CIE 1931 (X, Y, Z) color system measured from the glass surface is preferably 0.23≦x≦0.36 and 0.24≦y≦0.36, and more preferably 0.26≦x≦0.36 and 0.28≦y≦0.36.

[0066] The light transmittance of the colored film can be measured using an ultraviolet-visible-near-infrared spectrophotometer by forming a coating film of the colored resin composition on a transparent substrate, drying the coating film using a hot plate or the like, and then heating it in a hot air oven or the like to obtain a colored film, using the light transmittance of the transparent substrate as a reference. As described above, in the colored film, the crosslinkable groups contained in the resin (A) in the colored resin composition are preferably crosslinked by heat and / or light and substantially no longer remain. For example, when the colored resin composition contains an acrylic resin as the resin (A), the heat treatment temperature is preferably 170°C or higher, and the heat treatment time is preferably 30 minutes or longer. As the ultraviolet-visible spectrophotometer, UV-3150 (manufactured by Shimadzu Corporation) is preferred, and as the transparent substrate, Tempax (manufactured by AGC Technoglass Co., Ltd.), a translucent glass substrate, is preferred. The OD value of a coating film or a colored film can be calculated by measuring the intensity of incident light and transmitted light of the coating film or the colored film using an optical densitometer (361T Visual; manufactured by X-Rite Corporation) and using the following formula (3): OD value = log １０ (I ０ / I) Formula (3) I ０ : Incident light intensity I: Transmitted light intensity.

[0067] The optical density (OD value) of the colored film obtained from the colored resin composition of the present invention is preferably 0.5 or more, more preferably 0.7 or more, per 1 μm of film thickness. The higher the OD value per unit film thickness, that is, the lower the transmittance in the visible light region, the thinner the film thickness of the colored film that can achieve the desired visible light blocking properties can be.

[0068] The colored resin composition of the present invention was formed into a colored film on a non-alkali glass having a thickness of 0.7 mm so that the OD value was 4. The colored film was measured from the glass surface by the SCI method according to CIE1976 (L ＊ , a ＊ , b ＊ Reflection chromaticity value (a ＊ , b ＊ ) is -0.5≦a * ≦1.0 and −1.0≦b * ≦0.5, and 0.0≦a * ≦1.0 and −1.0≦b* It is more preferable that the reflection chromaticity is ≦0.0. The reflection chromaticity is an index of the color tone of the image reflected on the colored film, and in the SCI system (a ＊ , b ＊ On the other hand, the reflection color tone of a liquid crystal display device or an organic EL display when it is not lit is generally the b ＊ is a negative value and has a bluish color tone, so b is not suitable for use as a decorative film for a display device. ＊ It is preferable that the value of the colored film formed in the same manner is negative. ＊ , a ＊ , b ＊ ) color system reflectance chromaticity value (L ＊ ) but L ＊ It is preferable that L≦3.0. ＊ It is more preferable that the (L ＊ ) is an index showing the diffuse reflectance, and (L ＊ The closer the value is to 0.0, the more jet black the reflection color tone is, and a jet black reflection color tone is preferable from the standpoint of design.

[0069] Colorimetric values ​​(color values) measured by a colorimeter are significantly affected by the geometric conditions of illumination and light reception. Colorimeter geometric conditions are broadly divided into 45-degree illumination systems and diffuse illumination systems using an integrating sphere. Diffuse illumination systems are further divided into SCI (Specular Component Include) and SCE (Specular Component Exclude) systems depending on the method used to process the specular reflection component using a light trap. In SCI, all specular reflection components from the sample are integrated. In SCE, on the other hand, the specular reflection component is removed by a light trap installed on the wall of the integrating sphere, so the diffuse reflection component is measured.

[0070] Reflection chromaticity of the colored film (L ＊ , a ＊ , b ＊The color chromaticity (SCI) and diffuse reflection chromaticity (SCE) of light incident from a transparent substrate are measured using a spectrophotometer (CM-2600d; manufactured by Konica Minolta, Inc.) calibrated with a white calibration plate (CM-A145; manufactured by Konica Minolta, Inc.) under the measurement conditions of standard illuminant D65 (color temperature 6504K), a viewing angle of 2° (CIE1976), atmospheric pressure, and 20°C.

[0071] A preferred method for producing the colored resin composition of the present invention is, for example, to disperse a resin solution containing (A) resin, (B) colorant, and (C) organic solvent using a disperser to prepare a colorant dispersion liquid with a high colorant concentration in advance, and then to add (A) resin and, if necessary, other components such as a photosensitizer, followed by stirring. Filtration may be performed if necessary.

[0072] In the present invention, it is preferable to use a pigment that has been subjected to a pre-atomization treatment as the colorant (B). Examples of means for atomizing the pigment include a salt milling treatment in which the pigment, an inorganic salt, and an organic solvent are kneaded and milled, and an acid slurry treatment in which the pigment is first dissolved in a strong acid such as sulfuric acid and then mixed with a poor solvent.

[0073] A preferred salt milling treatment is a method in which a pigment, a water-soluble inorganic salt, and an organic solvent that does not dissolve the inorganic salt are kneaded, the kneaded mixture is then poured into water, and the resulting slurry is filtered and washed with water to remove the inorganic salt. A resin such as a polymer dispersant or a pigment derivative may be added together with the pigment, the water-soluble inorganic salt, and the organic solvent, which can prevent the pigment from re-aggregating after atomization by the salt milling treatment.

[0074] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, calcium chloride, barium chloride, and sodium sulfate.

[0075] The organic solvent is not particularly limited as long as it is water-soluble and does not dissolve water-soluble inorganic salts. However, since the temperature rises during salt milling and the organic solvent becomes prone to evaporation, a high-boiling point solvent is preferred from the standpoint of safety. Examples include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl glycol, 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, and low-molecular-weight polypropylene glycol. Two or more of these may be used.

[0076] Examples of kneading devices include kneaders, mix mullers, planetary mixers such as "Trimix" (registered trademark) manufactured by Inoue Seisakusho Co., Ltd., and continuous uniaxial kneaders such as "Miracle KCK" (registered trademark) manufactured by Asada Iron Works Co., Ltd.

[0077] Examples of dispersing machines for dispersing a resin solution containing (A) resin, (B) colorant, and (C) organic solvent include ball mills, bead mills, sand grinders, three-roll mills, and high-speed impact mills. Among these, bead mills are preferred for improving dispersion efficiency and achieving fine dispersion. Examples of bead mills include co-ball mills, basket mills, pin mills, and dyno mills. Examples of beads for bead mills include titania beads, zirconia beads, and zircon beads.

[0078] In the present invention, multi-stage dispersion using a bead mill is preferred, and preferably includes a step of dispersing using a bead mill with beads having an average bead diameter greater than 0.1 mmφ, followed by a step of dispersing using a bead mill with beads having an average bead diameter of 0.1 mmφ or less. Dispersing using a bead mill with beads having an average bead diameter greater than 0.1 mmφ can efficiently disintegrate pigments with large crystallite sizes. Subsequent dispersion using a bead mill with fine beads having an average bead diameter of 0.1 mmφ or less reduces the energy applied to the pigment, allowing for fine dispersion while maintaining the pigment's surface activity, thereby suppressing re-aggregation of the pigment in the colored resin composition and achieving a more uniform dispersion. In this case, the bead mill is preferably equipped with a centrifugal separator capable of separating the fine beads from the dispersion. Here, the average bead diameter refers to the number-average value of the equivalent circle diameters of the beads. Specifically, the beads are photographed at 45x magnification using a stereomicroscope, and the longest and shortest diameters of 100 randomly selected beads are measured, the average of which is taken as the equivalent circle diameter, and the number-average value is calculated to determine the bead diameter.

[0079] A colored film can be obtained by forming the colored resin composition of the present invention into a film. Specifically, a colored film can be obtained by applying the colored resin composition of the present invention to a transparent substrate such as glass, plastic, or film, and drying or distilling off the organic solvent if it contains an organic solvent, and optionally performing a curing reaction. The application method is not particularly limited, and examples thereof include silk screen printing, offset printing, pad printing, letterpress printing, gravure printing, inkjet printing, gravure coating, roll coating, reverse roll coating, roll doctor coating, bar coating, curtain flow coating, die coating, spin coating, air doctor coating, and spray coating, depending on the liquid properties of the substrate and the colored resin composition.

[0080] Next, an example of a method for forming a colored film using the colored resin composition of the present invention will be described, taking a negative photosensitive colored resin composition as an example.

[0081] A photosensitive colored resin composition is applied onto a substrate to obtain a coating film. Examples of the substrate include transparent substrates such as soda glass, alkali-free glass, and quartz glass; silicon wafers, ceramics, and gallium arsenide substrates. Examples of the coating method include spin coating using a spinner, spray coating, inkjet coating, die coating, and roll coating. The thickness of the coating film can be appropriately selected depending on the coating method, etc. The film thickness after drying is generally 1 to 150 μm.

[0082] The resulting coating film is dried to obtain a dried film. Drying methods include, for example, heat drying, air drying, reduced pressure drying, and infrared irradiation. Heat drying devices include, for example, ovens and hot plates. The drying temperature is preferably 50 to 150°C, and the drying time is preferably 1 minute to several hours.

[0083] The resulting dried film is irradiated with actinic rays through a mask having a desired pattern to obtain an exposed film. Examples of the actinic rays to be irradiated include ultraviolet rays, visible light, electron beams, and X-rays. The colored resin composition of the present invention is preferably irradiated with i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp.

[0084] The resulting exposed film is developed using an alkaline developer or the like to remove the unexposed areas, thereby obtaining a pattern. Examples of alkaline compounds used in alkaline developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous 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; and cyclic amines such as pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane, and morpholine.

[0085] The concentration of the alkaline compound in the alkaline developer is generally 0.01 to 50% by weight, preferably 0.02 to 3% by weight. Furthermore, to improve the pattern shape after development, 0.1 to 5% by weight of a surfactant such as a nonionic surfactant may be added. Furthermore, when the developer is an alkaline aqueous solution, a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be added to the developer.

[0086] Examples of the developing method include immersion, spray, puddle, etc. The resulting pattern may be rinsed with pure water or the like.

[0087] The resulting pattern can be subjected to a heat treatment (post-baking) to obtain a patterned colored film. The heat treatment may be carried out in air, a nitrogen atmosphere, or a vacuum. The heating temperature is preferably 150 to 300°C, and the heating time is preferably 0.25 to 5 hours. The heating temperature may be changed continuously or stepwise.

[0088] The colored resin composition and colored film of the present invention have high light-shielding properties in the visible light region and high transmittance in the near-infrared region, and the reflected color tone and transmitted color tone are achromatic. Therefore, they can be suitably used as colored films for decorative substrates in display terminals such as smartphones and tablet PCs, colored films for decorative panels for concealing near-infrared sensors and near-infrared cameras for driver monitoring and gesture sensors in in-vehicle displays and in-vehicle instruments, decorative films and resin molded products for concealing LiDAR sensors, colored films for icons in in-vehicle displays and in-vehicle instruments, light-shielding images such as black matrices in color filters provided in liquid crystal display devices and the like, and colored partition walls inside organic EL displays.

[0089] The decorated substrate of the present invention is a substrate that includes a substrate serving as a support for a colored film and the colored film of the present invention, and is decorated (including a single color) with the colored film of the present invention. Examples of the decorated substrate include cover glass substrates for smartphones, tablet PCs, and in-vehicle displays, and cover lens substrates for concealing near-infrared cameras or near-infrared sensors.

[0090] The present invention will be described in detail below with reference to specific examples, but the present invention should not be construed as being limited to these examples.

[0091] <Evaluation Method> [Pigment Crystallite Size] The colored resin composition was applied to a 0.7 mm thick alkali-free glass substrate (AN100) using a spinner (1H-DS) manufactured by Mikasa Co., Ltd., and the applied film was heated and dried on a hot plate at 100°C for 2 minutes. The dried film was post-baked in a hot air oven at 230°C for 30 minutes to obtain a colored film, which was then scraped off from the glass plate and packed into an aluminum standard sample holder. The X-ray diffraction spectrum of this sample was measured by wide-angle X-ray diffraction using a DS ADVANCE (trade name) X-ray diffractometer manufactured by Bruker AXS Co., Ltd., with CuKα radiation as the X-ray source. 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 of the resulting main peak were measured, and the crystallite size was calculated using the Scherrer equation represented by the above formula (1).

[0092] The azomethine pigment Bk-1 described in Production Example 1 exhibits a main peak with the strongest intensity at a diffraction angle 2θ of 26.25° or more and 26.45° or less, and the bisbenzofuranone pigment Bk-2 described in Production Example 2 exhibits a main peak with the strongest intensity at a diffraction angle 2θ of 7.80° or more and 8.00° or less.

[0093] [Light-shielding property] The OD value per 1 μm of film thickness of the colored film was calculated using an optical densitometer 361T Visual manufactured by X-Rite Corporation.

[0094] [Visible Light Transmission Chromaticity and Near-Infrared Transmittance] For a colored film formed by adjusting the OD value to 1.0, the transmittance was measured at wavelengths of 380 nm to 780 nm using a UV-3150 ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation, and the transmission chromaticity (x, y) was also determined. For a colored film formed by adjusting the OD value to 4.0, the transmittance was similarly measured at wavelengths of 920 nm to 960 nm, and the average transmittance was determined. The higher the average transmittance, the better the light transmittance in the near-infrared region. Note that the transmittance shown in the table represents the value for the colored film only, and the transmittance was measured using the substrate as a reference.

[0095] [Near-infrared camera images] For the colored film, an infrared camera module Freemo manufactured by Alpha Technology was placed on the back of the colored film, and the obtained camera images were evaluated based on the following criteria: A: A clear image can be confirmed B: An image can be confirmed, but the outline is unclear C: An image cannot be confirmed.

[0096] [Reflected chromaticity] The colored film was adjusted to have an OD value of 4.0, and the total reflected chromaticity (SCI) and diffuse reflected chromaticity (SCE) of light incident from a transparent substrate were measured using a spectrophotometer (CM-2600d; manufactured by Konica Minolta, Inc.) calibrated with a white calibration plate (CM-A145; manufactured by Konica Minolta, Inc.) under the following measurement conditions: standard illuminant D65 (color temperature 6504K), viewing angle 2° (CIE1976), atmospheric pressure, and 20°C. ＊ , a ＊ , b ＊ ) was evaluated.

[0097] Synthesis Example 1: Synthesis of Acrylic Resin (P-1) A methyl methacrylate / methacrylic acid / styrene copolymer (weight ratio 30 / 40 / 30) was synthesized by the method described in Example 1 of Japanese Patent No. 3,120,476. 40 parts by weight of glycidyl methacrylate was added to 100 parts by weight of the obtained copolymer, and the mixture was reprecipitated with purified water, filtered, and dried to obtain an acrylic resin (P-1) having a weight average molecular weight of 15,000 and an acid value of 110 mgKOH / g. The acid value of the acrylic resin was defined as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic resin (unit: mgKOH / g). The weight average molecular weight was measured using a gel permeation chromatography (GPC) "HLC-8220GPC" (testing equipment manufactured by Tosoh Corporation) as a carrier, converted to polystyrene.

[0098] (Production Example 1: Production of Azomethine Pigment Bk-1) Chromofine Black A1103 manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. as an azomethine pigment, 2400 g of sodium chloride, and 400 g of diethylene glycol were charged into a kneader (S-type kneader (trade name) manufactured by Moriyama Seisakusho Co., Ltd.) and kneaded for 8 hours at 70° C. Next, this kneaded mixture was charged into approximately 10 L of warm water, and stirred for 1 hour with a high-speed mixer while heating to 40° C. to form a slurry, which was then filtered and washed with water to remove the sodium chloride and diethylene glycol, and then vacuum dried at 80° C. for 24 hours to obtain azomethine pigment Bk-1.

[0099] (Production Example 2: Production of Bisbenzofuran Pigment Bk-2) "Irgaphor" Black S0100CF manufactured by BASF Corporation as a bisbenzofuran pigment, 2400 g of sodium chloride, and 400 g of diethylene glycol were charged into a kneader (S-type kneader (trade name) manufactured by Moriyama Seisakusho Co., Ltd.) and kneaded for 8 hours at 70°C. Next, this kneaded mixture was charged into approximately 10 L of warm water, and stirred for 1 hour with a high-speed mixer while heating to 40°C to form a slurry, which was then filtered and washed with water to remove the sodium chloride and diethylene glycol, and then vacuum dried at 80°C for 24 hours to obtain bisbenzofuran pigment Bk-2.

[0100] (Production Example 3: Production of Blue Pigment PB15:6-1) 200 g of "LIONOL BLUE ES" (PB15:6) manufactured by Toyocolor Co., Ltd., 2,400 g of sodium chloride, and 400 g of diethylene glycol were charged into a kneader (S-type kneader (trade name) manufactured by Moriyama Seisakusho Co., Ltd.) and kneaded for 8 hours at 70° C. Next, this kneaded mixture was charged into approximately 10 L of warm water, and stirred for 1 hour with a high-speed mixer while heating to 40° C. to form a slurry, which was then filtered and washed with water to remove the sodium chloride and diethylene glycol, and then vacuum dried at 80° C. for 24 hours to obtain a blue pigment PB15:6-1.

[0101] (Production Example 4: Production of Red Pigment PR177-1) A red pigment PR177-1 was obtained in the same manner as in Production Example 3, except that "Chromophtal Red A3B" (PR177) manufactured by BASF Corporation was used instead of "LIONOL BLUE ES" (PB15:6) manufactured by Toyocolor Co., Ltd.

[0102] (Production Example 5: Production of Yellow Pigment PY150-1) A yellow pigment PY150-1 was obtained in the same manner as in Production Example 3, except that "E-4GN" (PY150) manufactured by LANXESS K.K. was used instead of "LIONOL BLUE ES" (PB15:6) manufactured by TOYOCOLOR CO., LTD.

[0103] (Production Example 6: Production of Colorant Dispersion Liquid (D-1)) 120 g of the azomethine pigment Bk-1, 171 g of a 35 wt % solution of the acrylic resin (P-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA), 20 g of a polyamide polymer dispersant "DISPERBYK" 2200 (BYK-2200) as a polymer dispersant, and 689 g of PGMEA were charged into a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion liquid. The obtained preliminary dispersion was supplied to a disperser Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd., equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.30 mmφ, and dispersion was carried out for 20 minutes at a rotation speed of 12 m / s. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mmφ, and dispersion was carried out for 90 minutes at a rotation speed of 8 m / s, thereby obtaining a colorant dispersion D-1 having a solids concentration of 20% by weight and a colorant / (resin+dispersant) (weight ratio) of 60 / 40.

[0104] (Production Example 7 Production of Colorant Dispersion (D-2)) 120 g of azomethine pigment Bk-1, 171 g of a 35 wt% solution of propylene glycol monomethyl ether acetate (PGMEA) of the acrylic resin (P-1) obtained in Synthesis Example 1, 20 g of the polyamide polymer dispersant "DISPERBYK" 2200 (BYK-2200) as a polymer dispersant, and 689 g of PGMEA were charged into a tank and stirred with a homomixer for 20 minutes to obtain a preliminary dispersion. Using zirconia beads with a bead diameter of 1.00 mmφ, the mixture was dispersed for 3 hours using a paint shaker (Toyo Seiki Seisakusho, Ltd.), and then filtered through a 5 μm filter to obtain colorant dispersion D-2 with a solids concentration of 20 wt% and a colorant / (resin + polymer dispersant) (weight ratio) of 60 / 40.

[0105] (Production Example 8: Production of Colorant Dispersion Liquid (D-3)) A colorant dispersion liquid D-3 having a solid content concentration of 20% by weight and a colorant / (resin+dispersant) (weight ratio) of 60 / 40 was obtained in the same manner as in Production Example 6, except that the bisbenzofuran pigment Bk-2 was used instead of the azomethine pigment Bk-1.

[0106] (Production Example 9: Production of Colorant Dispersion Liquid (D-4)) A colorant dispersion liquid D-4 having a solid content concentration of 20% by weight and a colorant / (resin+dispersant) (weight ratio) of 60 / 40 was obtained in the same manner as in Production Example 7, except that the bisbenzofuran pigment Bk-2 was used instead of the azomethine pigment Bk-1.

[0107] (Production Example 10: Production of Colorant Dispersion Liquid (D-5)) 120 g of the blue pigment PB15:6-1, 171 g of a 35 wt % solution of the acrylic resin (P-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA), 20 g of an amine-based polymer dispersant "BYK LPN-21116" as a polymer dispersant, and 689 g of PGMEA were charged into a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion liquid. The obtained preliminary dispersion was supplied to a disperser Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd., equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.50 mmφ, and dispersion was carried out for 20 minutes at a rotation speed of 12 m / s. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.05 mmφ, and dispersion was carried out for 90 minutes at a rotation speed of 8 m / s, thereby obtaining a colorant dispersion D-5 having a solids concentration of 20% by weight and a colorant / (resin + polymer dispersant) (weight ratio) = 60 / 40.

[0108] (Production Example 11 Production of Colorant Dispersion Liquid (D-6)) A colorant dispersion liquid D-6 having a solid content concentration of 20% by weight and a colorant / (resin+dispersant) (weight ratio) of 60 / 40 was obtained in the same manner as in Production Example 10, except that the red pigment PR177-1 was used instead of the blue pigment PB15:6-1.

[0109] (Production Example 12 Production of Colorant Dispersion Liquid (D-7)) A colorant dispersion liquid D-7 having a solid content concentration of 20% by weight and a colorant / (resin+dispersant) (weight ratio) of 60 / 40 was obtained in the same manner as in Production Example 10, except that the yellow pigment PY150-1 was used instead of the blue pigment PB15:6-1.

[0110] (Production Example 13 Production of Colorant Dispersion Liquid (D-8)) 120 g of the azomethine pigment Bk-1, 171 g of a 35 wt % solution of the acrylic resin (P-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA), 20 g of a polyamide polymer dispersant "DISPERBYK" 2200 (BYK-2200) as a polymer dispersant, and 689 g of PGMEA were charged into a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion liquid. The obtained preliminary dispersion was supplied to a disperser Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd., equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.30 mmφ, and dispersion was carried out for 20 minutes at a rotation speed of 12 m / s. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.10 mmφ, and dispersion was carried out for 90 minutes at a rotation speed of 8 m / s, thereby obtaining a colorant dispersion D-8 having a solids concentration of 20% by weight and a colorant / (resin + dispersant) (weight ratio) of 60 / 40.

[0111] (Production Example 14 Production of Colorant Dispersion Liquid (D-9)) 120 g of the azomethine pigment Bk-1, 171 g of a 35 wt % solution of the acrylic resin (P-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA), 20 g of a polyamide polymer dispersant "DISPERBYK" 2200 (BYK-2200) as a polymer dispersant, and 689 g of PGMEA were charged into a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion liquid. The obtained preliminary dispersion was supplied to a disperser Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd., equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.30 mmφ, and dispersion was carried out for 20 minutes at a rotation speed of 12 m / s. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.03 mmφ, and dispersion was carried out for 90 minutes at a rotation speed of 8 m / s, thereby obtaining a colorant dispersion D-9 having a solids concentration of 20% by weight and a colorant / (resin + dispersant) (weight ratio) of 60 / 40.

[0112] (Production Example 15 Production of Colorant Dispersion Liquid (D-10)) A colorant dispersion liquid D-10 having a solid content concentration of 20% by weight and a colorant / (resin+dispersant) (weight ratio) of 60 / 40 was obtained in the same manner as in Production Example 14, except that the bisbenzofuran pigment Bk-2 was used instead of the azomethine pigment Bk-1.

[0113] (Production Example 16: Production of Colorant Dispersion Liquid (D-11)) 120 g of the bisbenzofuran pigment Bk-2, 171 g of a 35 wt % solution of the acrylic resin (P-1) obtained in Synthesis Example 1 in propylene glycol monomethyl ether acetate (PGMEA), 20 g of a polyamide polymer dispersant "DISPERBYK" 2200 (BYK-2200) as a polymer dispersant, and 689 g of PGMEA were charged into a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion liquid. The obtained preliminary dispersion was supplied to a disperser Ultra Apex Mill UAM015 manufactured by Kotobuki Industries Co., Ltd., equipped with a centrifugal separator filled with 75% by volume of zirconia beads having a bead diameter of 0.30 mmφ, and dispersion was carried out for 20 minutes at a rotation speed of 12 m / s. Subsequently, the liquid after the dispersion treatment was supplied to an Ultra Apex Mill UAM015 filled with 75% by volume of zirconia beads having a bead diameter of 0.02 mmφ, and dispersion was carried out for 90 minutes at a rotation speed of 8 m / s, thereby obtaining a colorant dispersion D-11 having a solid content concentration of 20% by weight and a colorant / (resin+dispersant) (weight ratio) of 60 / 40.

[0114] The compositions and dispersion conditions of the colorant dispersions of Production Examples 6 to 16 are shown in Table 1.

[0115]

[0116] (Example 1) To a mixture of 21.67 g of colorant dispersion liquid (D-1) and 5.42 g of colorant dispersion liquid (D-3), 31.04 g of a 35 wt% solution of acrylic polymer (P-1) in PGMEA, 8.33 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver, and 0.30 g of a 10 wt% solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant. A solution obtained by dissolving 0.30 g of a 10 wt% solution of PGMEA in 32.90 g of PGMEA was added, to obtain a colored resin composition PC-1 having a total solids concentration of 25 wt%, and a colorant content of 13 parts by weight relative to 100 parts by weight of the total solids.

[0117] The obtained colored resin composition PC-1 was applied to a 0.7 mm thick alkali-free glass substrate (AN100) using a spinner (1H-DS) manufactured by Mikasa Co., Ltd., and the applied film was heated and dried on a hot plate at 100 ° C. for 2 minutes. This dried film was post-baked in a hot air oven at 230 ° C. for 30 minutes to obtain a colored film C-1. The results of evaluation of this colored film C-1 by the above-mentioned method are shown in Table 2.

[0118] (Example 2) A colored resin composition PC-2 was obtained in the same manner as in Example 1, except that the colorant dispersion liquid (D-1) was 20.31 g and the colorant dispersion liquid (D-3) was 6.77 g. Using the obtained colored resin composition PC-2, the same evaluations as in Example 1 were performed. The results are shown in Table 2.

[0119] (Example 3) A colored resin composition PC-3 was obtained in the same manner as in Example 1, except that the colorant dispersion liquid (D-1) was 13.54 g and the colorant dispersion liquid (D-3) was 13.54 g. Using the obtained colored resin composition PC-3, evaluations were carried out in the same manner as in Example 1. The results are shown in Table 2. The X-ray diffraction spectrum of the obtained colored film is also shown in Figure 1.

[0120] (Example 4) A colored resin composition PC-4 was obtained in the same manner as in Example 1, except that the colorant dispersion liquid (D-1) was 9.48 g and the colorant dispersion liquid (D-3) was 17.60 g. Using the obtained colored resin composition PC-4, the same evaluations as in Example 1 were performed. The results are shown in Table 2.

[0121] (Example 5) A colored resin composition PC-5 was obtained in the same manner as in Example 1, except that the colorant dispersion liquid (D-1) was 6.77 g and the colorant dispersion liquid (D-3) was 20.31 g. Using the obtained colored resin composition PC-5, the same evaluations as in Example 1 were performed. The results are shown in Table 2.

[0122] (Example 6) To a mixture of 41.67 g of colorant dispersion (D-1) and 10.42 g of colorant dispersion (D-3), 20.73 g of a 35 wt% solution of acrylic polymer (P-1) in PGMEA, 6.92 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver, and 0.30 g of a 10 wt% solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie) in PGMEA was dissolved in 19.59 g of PGMEA to obtain a colored resin composition PC-6 having a total solids concentration of 25 wt% and a colorant content of 25 parts by weight per 100 parts by weight of total solids. Using the obtained colored resin composition PC-6, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

[0123] (Example 7) A colored resin composition PC-7 was obtained in the same manner as in Example 6, except that the colorant dispersion liquid (D-1) was 39.06 g and the colorant dispersion liquid (D-3) was 13.02 g. Using the obtained colored resin composition PC-7, the same evaluations as in Example 1 were performed. The results are shown in Table 2.

[0124] (Example 8) A colored resin composition PC-8 was obtained in the same manner as in Example 6, except that the colorant dispersion liquid (D-1) was 26.04 g and the colorant dispersion liquid (D-3) was 26.04 g. Using the obtained colored resin composition PC-8, the same evaluations as in Example 1 were performed. The results are shown in Table 2.

[0125] (Example 9) A colored resin composition PC-9 was obtained in the same manner as in Example 6, except that the colorant dispersion liquid (D-1) was 18.23 g and the colorant dispersion liquid (D-3) was 33.85 g. Using the obtained colored resin composition PC-9, the same evaluations as in Example 1 were performed. The results are shown in Table 2.

[0126] (Example 10) A colored resin composition PC-10 was obtained in the same manner as in Example 4, except that the colorant dispersion liquid (D-1) was 13.02 g and the colorant dispersion liquid (D-3) was 39.06 g. Using the obtained colored resin composition PC-10, the same evaluations as in Example 1 were performed. The results are shown in Table 2.

[0127] (Example 11) To a mixture of 10.00 g of colorant dispersion (D-1) and 2.50 g of colorant dispersion (D-3), 37.02 g of a 35 wt% solution of acrylic polymer (P-1) in PGMEA, 9.14 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver, and 0.30 g of a 10 wt% solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie) in PGMEA was dissolved in 40.67 g of PGMEA to obtain a colored resin composition PC-11 having a total solids concentration of 25 wt% and a colorant content of 6 parts by weight relative to 100 parts by weight of the total solids. Using the obtained colored resin composition PC-11, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

[0128] (Example 12) A colored resin composition PC-12 was obtained in the same manner as in Example 11, except that the colorant dispersion liquid (D-1) was 9.38 g and the colorant dispersion liquid (D-3) was 3.13 g. Using the obtained colored resin composition PC-12, the same evaluations as in Example 1 were performed. The results are shown in Table 2.

[0129] (Example 13) A colored resin composition PC-13 was obtained in the same manner as in Example 11, except that the colorant dispersion liquid (D-1) was 6.25 g and the colorant dispersion liquid (D-3) was 6.25 g. Using the obtained colored resin composition PC-13, the same evaluations as in Example 1 were performed. The results are shown in Table 2.

[0130] (Example 14) A colored resin composition PC-14 was obtained in the same manner as in Example 11, except that the colorant dispersion liquid (D-1) was 4.38 g and the colorant dispersion liquid (D-3) was 8.13 g. Using the obtained colored resin composition PC-14, the same evaluations as in Example 1 were performed. The results are shown in Table 2.

[0131] (Example 15) A colored resin composition PC-15 was obtained in the same manner as in Example 11, except that the colorant dispersion liquid (D-1) was 3.13 g and the colorant dispersion liquid (D-3) was 9.38 g. Using the obtained colored resin composition PC-15, the same evaluations as in Example 1 were performed. The results are shown in Table 2.

[0132] (Example 16) To a mixture of 31.25 g of colorant dispersion (D-1) and 31.25 g of colorant dispersion (D-3), 16.45 g of a 35 wt% solution of acrylic polymer (P-1) in PGMEA, 6.34 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver, and 0.30 g of a 10 wt% solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie) in PGMEA was dissolved in 14.04 g of PGMEA to obtain a colored resin composition PC-16 having a total solids concentration of 25 wt% and a colorant content of 30 parts by weight relative to 100 parts by weight of the total solids. Using the obtained colored resin composition PC-16, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

[0133] (Example 17) To a mixture of 36.46 g of colorant dispersion (D-1) and 36.46 g of colorant dispersion (D-3), 12.16 g of a 35 wt% solution of acrylic polymer (P-1) in PGMEA, 5.75 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver, and 0.30 g of a 10 wt% solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie) in PGMEA was dissolved in 8.49 g of PGMEA to obtain a colored resin composition PC-17 having a total solids concentration of 25 wt% and a colorant content of 35 parts by weight relative to 100 parts by weight of the total solids. Using the obtained colored resin composition PC-17, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

[0134] (Example 18) To a mixture of 40.63 g of colorant dispersion (D-1) and 40.63 g of colorant dispersion (D-3), 8.73 g of a 35 wt% solution of acrylic polymer (P-1) in PGMEA, 5.29 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver, and 0.30 g of a 10 wt% solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie Co., Ltd.) in PGMEA was dissolved in 4.05 g of PGMEA to obtain a colored resin composition PC-18 having a total solids concentration of 25 wt% and a colorant content of 35 parts by weight relative to 100 parts by weight of the total solids. Using the obtained colored resin composition PC-18, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

[0135] (Example 19) A colored resin composition PC-19 was obtained in the same manner as in Example 3, except that the colorant dispersion liquid (D-2) was used instead of the colorant dispersion liquid (D-1). The obtained colored resin composition PC-19 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0136] (Example 20) A colored resin composition PC-20 was obtained in the same manner as in Example 3, except that the colorant dispersion liquid (D-4) was used instead of the colorant dispersion liquid (D-3). The obtained colored resin composition PC-20 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0137] (Example 21) 12.19 g of colorant dispersion liquid (D-1), 12.19 g of colorant dispersion liquid (D-3), and 2.71 g of colorant dispersion liquid (D-5) were mixed, and 31.02 g of a 35 wt% solution of acrylic polymer (P-1) in PGMEA, 8.32 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver, and 0.30 g of a 10 wt% solution of silicone surfactant "BYK" 333 (manufactured by BYK Chemie Co., Ltd.) as a surfactant was dissolved in 32.90 g of PGMEA to obtain a colored resin composition PC-21 having a total solids concentration of 25 wt%, and a colorant content of 13 parts by weight relative to 100 parts by weight of the total solids. The obtained colored resin composition PC-21 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0138] (Example 22) 23.44 g of colorant dispersion liquid (D-1), 23.44 g of colorant dispersion liquid (D-3), and 5.21 g of colorant dispersion liquid (D-5) were mixed, and 20.73 g of a 35 wt% solution of acrylic polymer (P-1) in PGMEA, 6.92 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver, and 0.30 g of a 10 wt% solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie Co., Ltd.) as a surfactant was dissolved in 19.59 g of PGMEA to obtain a colored resin composition PC-22 having a total solids concentration of 25 wt%, and a colorant content of 25 parts by weight relative to 100 parts by weight of the total solids. The obtained colored resin composition PC-22 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0139] (Example 23) A colored resin composition PC-23 was obtained in the same manner as in Example 21, except that the colorant dispersion liquid (D-6) was used instead of the colorant dispersion liquid (D-5). The obtained colored resin composition PC-23 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0140] (Example 24) A colored resin composition PC-24 was obtained in the same manner as in Example 24, except that the colorant dispersion liquid (D-7) was used instead of the colorant dispersion liquid (D-5). The obtained colored resin composition PC-24 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0141] (Example 25) A colored resin composition PC-25 was obtained in the same manner as in Example 18, except that the colorant dispersion liquid (D-8) was used instead of the colorant dispersion liquid (D-1). The obtained colored resin composition PC-25 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0142] (Example 26) A colored resin composition PC-26 was obtained in the same manner as in Example 18, except that the colorant dispersion liquid (D-10) was used instead of the colorant dispersion liquid (D-3). The obtained colored resin composition PC-26 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0143] (Example 27) A colored resin composition PC-27 was obtained in the same manner as in Example 18, except that the colorant dispersion liquid (D-9) was used instead of the colorant dispersion liquid (D-1). The obtained colored resin composition PC-27 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0144] (Example 28) A colored resin composition PC-28 was obtained in the same manner as in Example 18, except that the colorant dispersion liquid (D-11) was used instead of the colorant dispersion liquid (D-3). The obtained colored resin composition PC-28 was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0145] (Comparative Example 1) To a mixture of 41.67 g of colorant dispersion (D-1) and 41.67 g of colorant dispersion (D-3), 7.88 g of a 35 wt% solution of acrylic polymer (P-1) in PGMEA, 5.17 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 0.38 g of KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver, and 0.30 g of a 10 wt% solution of silicone surfactant "BYK" 333 (manufactured by BYK-Chemie) in PGMEA was dissolved in 2.94 g of PGMEA to obtain a colored resin composition PC-29 having a total solids concentration of 25 wt% and a colorant content of 40 parts by weight per 100 parts by weight of the total solids. Using the obtained colored resin composition PC-29, evaluations were performed in the same manner as in Example 1. The results are shown in Table 2.

[0146] (Comparative Example 2) A colored resin composition PC-30 was obtained in the same manner as in Example 1, except that the colorant dispersion liquid (D-1) was 24.38 g and the colorant dispersion liquid (D-3) was 2.71 g. Using the obtained colored resin composition PC-30, the same evaluations as in Example 1 were carried out. The results are shown in Table 2.

[0147] (Comparative Example 3) A colored resin composition PC-31 was obtained in the same manner as in Example 1, except that the amount of colorant dispersion (D-1) was 2.71 g and the amount of colorant dispersion (D-3) was 24.38 g. Using the obtained colored resin composition PC-31, evaluations were performed in the same manner as in Example 1. The results are shown in Table 2.

[0148]

[0149]

[0150]

[0151] It can be seen that the colored resin compositions of the examples have high visible light blocking properties and near-infrared transmittance at a film thickness where the OD value is 4.0, and also have good reflected chromaticity. It can also be seen that the transmitted chromaticity is good at a film thickness where the OD value is 1.0. On the other hand, the colored resin compositions having a high content ratio of colorant in the total solid components have a low reflected chromaticity. ＊The values ​​were large, and the image reflected in the colored film was reddish. On the other hand, the colored resin composition in which the ratio of azomethine pigment to the total amount of coloring material was high had large x and y values ​​of transmitted chromaticity, and the transmitted color of the colored film was yellowish. On the other hand, the colored resin composition in which the ratio of bisbenzofuranone pigment to the total amount of coloring material was high had small x and y values ​​of transmitted chromaticity, and the transmitted color of the colored film was bluish.

[0152] The colored resin composition of the present invention can be suitably used 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 type icons.

Claims

1. A colored resin composition containing (A) a resin and (B) a colorant, wherein the (B) colorant contains at least an azomethine-based pigment and a bisbenzofuranone-based pigment. When the total weight of all colorants is 100 parts by weight, the content of the azomethine-based pigment is 25 to 80 parts by weight, and the content of the bisbenzofuranone-based pigment is 20 to 75 parts by weight, and the content of the (B) colorant is 1 to 39 parts by weight with respect to 100 parts by weight of the total content of solid components. A colored resin composition.

2. The colored resin composition according to claim 1, wherein the crystallite size of the azomethine-based pigment determined by the following measurement method is 10 nm or more and 25 nm or less. <Measurement method of crystallite size> Scrape off the film obtained by applying, drying, and heat-treating the colored resin composition on a glass substrate, and pack it in an aluminum standard sample holder. Using this sample, with the X-ray source as CuKα ray using an X-ray diffractometer, measure the X-ray diffraction spectrum by the wide-angle X-ray diffraction method. The measurement conditions are: output is 40 kV / 40 mA, slit system is Div. Slit: 0.3°, measurement step (2θ) is 0.0171°, and measurement time is 0.5 seconds / step. Measure the diffraction angle and half-value width of the main peak derived from the pigment, and obtain them using Scherrer's formula.

3. The colored resin composition according to claim 2, wherein the crystallite size of the bisbenzofuranone-based pigment determined by the measurement method of the crystallite size is 10 nm or more and 25 nm or less.

4. When the crystallite size of the azomethine-based pigment determined by the measurement method of the crystallite size is α (nm) and the crystallite size of the bisbenzofuranone-based pigment is β (nm), 3.0 ≦ |α - β| ≦ 10.

0. The colored resin composition according to claim 2 or 3, characterized by this.

5. The colored resin composition according to any one of claims 1 to 3, containing an alkali-soluble resin as the (A) resin, and further containing (D) a photosensitizer and (E) a radically polymerizable compound.

6. In a film formed on a non-alkali glass with a thickness of 0.7 mm so that the optical density (OD value) is 1, the transmission chromaticity (x, y) is 0.23 ≦ x ≦ 0.36 and 0.24 ≦ y ≦ 0.

36. The colored resin composition according to any one of claims 1 to 3.

7. In a film formed on an alkali-free glass with a thickness of 0.7 mm so as to have an optical density (OD value) of 4, the chromaticity values (a ＊ , b ＊ ) of the reflection chromaticity measured by the SCI method from the glass surface are such that -0.5 ≤ a ＊ ≤ 1.0 and -1.0 ≤ b ＊ ≤ 0.

5. The colored resin composition according to any one of claims 1 to 3.

8. A colored film containing (A) a resin and (B) a colorant, wherein at least an azomethine-based pigment and a bisbenzofuranone-based pigment are contained as the (B) colorant, and when the total weight of all colorants is 100 parts by weight, the content of the azomethine-based pigment is 25 to 80 parts by weight, and the content of the bisbenzofuranone-based pigment is 20 to 75 parts by weight, and the content of the (B) colorant is 1 to 39 parts by weight with respect to 100 parts by weight of the total content of solid components.

9. The colored film according to claim 8, wherein the crystallite size of the bisbenzofuranone-based pigment determined by the following measurement method is 10 nm or more and 25 nm or less. <Measurement method of crystallite size> Pack the colored film into an aluminum standard sample holder, and measure the X-ray diffraction spectrum of this sample by wide-angle X-ray diffraction method using an X-ray diffractometer with the X-ray source as CuKα ray. The measurement conditions are: output is 40 kV / 40 mA, slit system is Div. Slit: 0.3°, measurement step (2θ) is 0.0171°, and measurement time is 0.5 seconds / step. Measure the diffraction angle and half-value width of the main peak derived from the pigment, and obtain them using Scherrer's formula.

10. The colored film according to claim 9, wherein the crystallite size of the azomethine-based pigment determined by the above measurement method is 10 nm or more and 25 nm or less.

11. The colored film according to claim 9 or 10, wherein when the crystallite size of the azomethine-based pigment determined by the measurement method of the crystallite size is α (nm) and the crystallite size of the bisbenzofuranone-based pigment is β (nm), 3.0 ≦ |α - β| ≦ 10.

0.

12. The colored film according to any one of claims 8 to 10, wherein the transmission chromaticity (x, y) when the light is directly incident on the film surface of the colored film and converted to the film thickness corresponding to an optical density (OD value) of 1 is 0.23 ≦ x ≦ 0.36 and 0.24 ≦ y ≦ 0.

36.

13. The chromaticity values (a*, b*) of the reflectance chromaticity measured by the SCI method when the light is directly incident on the surface of the colored film and converted to a film thickness corresponding to an optical density (OD value) of 4 satisfy 0.0 ≦ a ＊ ≦ 1.0 and -1.0 ≦ b ＊ ≦ 0.

0. The colored film according to any one of claims 8 to 10

14. A decorative substrate comprising a substrate and the colored film according to any one of claims 8 to 10.