TW202336465A - Colored resin composition, colored film, and decorative substrate - Google Patents

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 compositions, colored films, decorative substrates

The present invention relates to a colored resin composition, a colored film that can be used as a near-infrared ray transmitting light-shielding film, and a decorative substrate.

In recent years, various biometric authentications have been adopted in various information terminals such as smartphones to enhance security. In addition to the conventional fingerprint verification, research on face verification and iris verification is also continuously developing. Near-infrared sensors or near-infrared cameras are used in facial verification or iris verification. In addition, in automobiles, 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) that serve as driving space sensors are also used. ) uses an infrared laser sensor. The above-mentioned near-infrared sensors or near-infrared cameras are generally placed in the decorative portion of the non-display area of various displays or the peripheral portion of the casing. However, since transparent or translucent covers have been used in the past, near-infrared rays can be seen from the outside. Sensors or near-infrared cameras have problems that impair their design. Therefore, the industry is studying a filter or colored film that has a high near-infrared transmittance and a low visible light transmittance to conceal the near-infrared sensor or near-infrared camera. From a design point of view, the reflected color of the filter or colored film is preferably close to the color of the display or the peripheral portion of the casing when not lit, and is particularly preferably achromatic black.

In addition, in the decorative part of the non-display area of the in-car display or the self-illuminating instrument, there are cases where a blackout display method is used. The above blackout display method is to display icons when the backlight is turned on. Hide, the icon appears not to exist when the backlight is off. In order to suppress the brightness of the icon when it is lit, or to improve the seamless feeling when it is not lit, a colored film with a visible light transmittance of 10 to 80% is sometimes formed on the icon portion. Since the transmitted light when the backlight is turned on is preferably achromatic, the transmitted color of the colored film formed for the purpose of black-view icon use is preferably achromatic.

Usually, the colored film that conceals near-infrared cameras and other icons and the colored film that forms the icon portion of the black-view mode are formed of different colored resin compositions. However, with the high functionality of in-car displays in recent years, the industry is studying a A design in which both a near-infrared camera and a black-view mode icon are installed in the frame decoration of a display. In this case, three types of decorative layers are required: a coloring film for sensor wiring concealment, a coloring film for near-infrared camera concealment, and a coloring film for icons. This increases the cost of printing processes and inks, which becomes a problem. Therefore, the industry desires a process for forming these three types of decorative layers using one colored resin composition.

For example, the industry has studied a colored resin composition that uses a bisbenzofuranone-based pigment as a coloring material and sets the crystallite size of the bisbenzofuranone-based pigment to a specific range (see, for example, Patent Document 1); and A composition for an infrared filter, which uses at least one selected from the group consisting of dibenzofuranone-based pigments, methimine-based pigments, and perylene-based pigments as a near-infrared ray-transmitting black color material, and thereby The total solid content contains 1 to 30% of a coloring material different from the near-infrared ray transmitting black coloring material (for example, refer to Patent Document 2). [Prior technical literature] [Patent Document]

Patent Document 1: International Publication No. 2019/230684 Patent Document 2: Japanese Patent Application Publication No. 2018-120248

(The problem that the invention wants to solve)

However, the colored film in the technology described in Patent Document 1 has excellent light resistance, high visible light shielding properties and high near-infrared ray transmittance, but its transmission chromaticity or reflection chromaticity is insufficient. In addition, the infrared transmission filter in the technology described in Patent Document 2 has high visible light shielding properties and has less noise from visible light components, but does not take transmission chromaticity or reflection chromaticity into consideration.

Therefore, an object of the present invention is to provide a colored resin composition that can form a colored film that has high visible light shielding properties and near-infrared ray transmittance, and further has excellent reflection tone and transmission tone. (Technical means to solve problems)

The present inventors conducted intensive research and found that by making the colored resin composition contain a resin and a coloring material, and containing a specific amount of a methimine-based pigment and a bisbenzofuranone-based pigment as the coloring material, The above-mentioned problems can be solved by setting the contents of all coloring materials within a specific range, leading to the completion of the present invention.

That is, the object of the present invention is mainly achieved by the following configuration. A colored resin composition containing (A) a resin and (B) a coloring material, and containing at least a methimine-based pigment and a bisbenzofuranone-based pigment as the above-mentioned (B) coloring material. When all the coloring materials are combined When the weight is set to 100 parts by weight, the content of the imine pigment is 25 to 80 parts by weight, and the content of the dibenzofuranone pigment is 20 to 75 parts by weight, and the content of the above-mentioned (B) coloring material is relatively The total content of solid components is 1 to 39 parts by weight based on 100 parts by weight. (Compare the effectiveness of previous technologies)

The colored resin composition of the present invention can obtain a colored film that is excellent in light transmittance in the near-infrared region (wavelength 800 to 1000 nm) and light-shielding property in the visible light region, and further has excellent reflection and transmission hues. With the colored resin composition of the present invention, excellent near-infrared camera images can be obtained, and a colored film with achromatic reflection and transmission tones and good design properties can be obtained.

Hereinafter, the present invention will be described in further detail.

The colored resin composition of the present invention contains (A) resin and (B) coloring material. (A) The resin functions as a binder in the composition, and (B) the coloring material functions to improve or adjust the optical properties, especially the shielding and absorbing properties of visible light. The colored resin composition of the present invention is characterized in that it contains at least a formimine-based pigment and a bisbenzofuranone-based pigment as the above-mentioned (B) coloring material. When the weight of all the coloring materials is 100 parts by weight, the formimide-based pigment is The content of the amine pigment is 25 to 80 parts by weight, and the content of the dibenzofuranone pigment is 20 to 75 parts by weight. In addition, in this specification, "~" indicating a numerical range includes the numerical values at both ends. Neutral reflective colors can be obtained by containing specific amounts of methimine-based pigments and dibenzofuranone-based pigments as (B) coloring materials, and setting the contents of all coloring materials in the total solid content to a specific range. Chroma and transparent color film. Furthermore, by dispersing the imine-based pigments and the bisbenzofuranone-based pigments in the colored resin composition and the colored film with a specific crystallite size, visible light can be blocked, and on the other hand, the near-infrared rays can be significantly increased. Transparency. In this way, clear near-infrared camera images can be obtained through the tinted film. In addition, the diffuse reflectance can be suppressed to a low level and a darker colored film with excellent design properties can be obtained. Furthermore, by further setting the difference between the crystallite size of the imine pigment and the crystallite size of the bisbenzofuranone pigment within a specific range, the visible light shielding property can be improved without changing the reflectance. Regarding the colored film obtained from the colored resin composition of the present invention, since the reflected chromaticity and transmitted chromaticity are achromatic, the diffuse reflectance is low, and it has high visible light shielding property and high near-infrared ray transmittance. It can be suitably used as a light-shielding film for concealing sensor wiring, a light-shielding film for concealing near-infrared cameras, and/or a light-shielding film for black-view mode icons.

Examples of the (A) resin include acrylic resin, Cardo resin, siloxane resin, polyimide resin, polyimide precursor, polyurethane resin, and polyester resin. , chlorine vinegar resin, etc. These may contain 2 or more types. Among them, from the viewpoint of the storage stability of the colored resin composition or the adhesion and reliability of the colored film, an acrylic resin, a polyurethane resin, or a polyester resin is preferred, and particularly preferred Acrylic resin.

The colored resin composition of the present invention may or may not have photosensitivity. By containing an alkali-soluble resin as the (A) resin and further containing the following (D) photosensitizer, the colored resin composition can be imparted with photosensitivity. sex. Here, the alkali-soluble resin refers to a resin having one or both groups of a hydroxyl group and a carboxyl group as an alkali-soluble group, an acid value of 10 mgKOH/g or more, and a weight average molecular weight (Mw) of 500 or more and 150,000 or less. Here, the weight average molecular weight (Mw) refers to a value calculated by analyzing by gel permeation chromatography using tetrahydrofuran as a carrier and converting it using a calibration curve obtained using standard polystyrene. In addition, the acid value of an alkali-soluble resin refers to the number of mg of potassium hydroxide required to neutralize 1 g of alkali-soluble resin (unit: mgKOH/g).

Examples of the alkali-soluble resin include cardo resin, acrylic resin, novolac resin, polyimide resin, polyimide precursor, and polybenzoyl resin. Azole resin, polybenzo Azole precursors, polyamide resins, siloxane resins and other resins having the above-mentioned alkali-soluble groups. When the colored resin composition has negative photosensitivity, from the viewpoint of pattern processability and coating film reliability, acrylic resin or polyimide resin is preferred; from the viewpoint of dispersion stability, More preferably, it contains acrylic resin. On the other hand, when the colored resin composition has positive photosensitivity, from the viewpoint of pattern processability, polyimide resin, polyimide precursor, polybenzo Azole resin, polybenzo Azole precursor and siloxane resin; from the viewpoint of pattern processability, it is more preferable to contain polyimide resin and polyimide precursor.

The colored resin composition of the present invention contains at least a formimine pigment and a bisbenzofuranone pigment as the (B) coloring material. When the weight of the coloring material (B) is 100 parts by weight, it is important to contain 25 to 80 parts by weight of the imine pigment and 20 to 75 parts by weight of the bisbenzofuranone pigment. By containing specific amounts of imine-based pigments and dibenzofuranone-based pigments as (B) coloring materials, and setting the contents of all coloring materials within a specific range, neutral reflection chromaticity and transmission chromaticity can be obtained Colored film. When the content of the imine-based pigment is less than 25 parts by weight, the transmitted chromaticity of the colored film shifts from achromatic to yellow, causing the transmitted light when the backlight is lit to be yellowish, which is undesirable. On the other hand, when the content of the imine-based pigment exceeds 80 parts by weight, the transmitted chromaticity of the colored film shifts from achromatic to blue, causing the transmitted light when the backlight is lit to be bluish, so it is not good. When the content of the dibenzofuranone-based pigment is less than 20 parts by weight, the transmitted chromaticity of the colored film shifts from achromatic to blue, causing the transmitted light to be bluish when the backlight is lit, which is undesirable. On the other hand, when the content of the dibenzofuranone-based pigment exceeds 75 parts by weight, the transmitted chromaticity of the colored film shifts from achromatic to yellow, causing the transmitted light when the backlight is lit to have a yellow color, so it is not good.

As a formimine pigment used in the present invention, as long as it has a formimine structure (RR'C=NR'') (R, R' are each independently hydrogen, or a fat that may contain heteroatoms such as nitrogen or oxygen. an aliphatic group or an aromatic group, R'' is an aliphatic group or an aromatic group that may contain heteroatoms such as nitrogen or oxygen), it can be used without particular restrictions. Specific examples include: Japanese Patent Application Laid-Open No. 1 -170601, Japanese Patent Application Laid-Open No. 2-34664, etc., for example, "Chromofine Black A1103" manufactured by Dainichi Seika Co., Ltd.

The bisbenzofuranone-based 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-based pigment may have two or more compounds containing these structures.

[Chemical 1]

In the general formulas (I) to (III), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ³ and R ⁴ independently represent R ¹⁰ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹¹ R ¹² , NR ¹¹ COR ¹² , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , CN , halogen atom or hydroxyl group. Wherein, R ¹⁰ represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms or a heterocyclic group with 2 to 20 carbon atoms, and R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an arylalkyl group with 7 to 30 carbon atoms, or a heterogeneous group with 2 to 20 carbon atoms. ring base. a and b each independently represent an integer from 0 to 4.

Bisbenzofuranone pigments having a structure represented by any one of the above general formulas (I) to (III) are known per se and can be obtained, for example, by the method described in Japanese Patent Publication No. 2012-515233. For example, it is commercially available as "Irgaphor" (registered trademark) Black S0100CF (trade name, manufactured by BASF Co., Ltd.).

The crystallite size of the pigment contained in the colored resin composition and the colored film can be determined based on the half-maximum width of the main peak with the strongest intensity observed in the X-ray diffraction spectrum when CuKα rays are used as the X-ray source. The crystallite size of the above-mentioned pigment is calculated from Scherrer's formula shown in the following formula (1).

[Number 1]

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

[Number 2]

β _e in the above formula (2) is the half-maximum width of the diffraction peak, and β _O is the correction value of the half-maximum width (0.13[°]). Among them, β, βe and β _O are calculated in radians.

X-ray diffraction spectroscopy uses the X-ray source as CuKα rays and is measured by the wide-angle X-ray diffraction method. As the X-ray diffraction device, DS ADVANCE manufactured by Bruker AXS Co., Ltd. or its equivalent is used. Regarding the measurement conditions, the output is 40 kV/40 mA, the slit system is Div. Slit: 0.3°, the measurement step distance (2θ) is 0.0171°, and the measurement time is 0.5 seconds/step.

Regarding the colored resin composition of the present invention, the colored resin composition is coated on a glass substrate, dried, and heated to obtain a film, and the obtained film is peeled off. According to the measurement of the above-mentioned X-ray diffraction spectrum, The crystallite size of the imine pigment, which is determined from the half-height width of the main peak, is preferably 10 nm or more and 25 nm or less, and more preferably 10 nm or more and 20 nm or less. The 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, in the colored film in the present invention, when the resin (A) in the colored resin composition contains a crosslinkable group, it is preferable that the crosslinkable group is crosslinked by heat and/or light and does not substantially remain. . The colored film can be obtained by forming a coating film of the colored resin composition on a transparent substrate, drying the coating film with a hot plate or the like, and then performing heat treatment with a hot air oven or the like. For example, when the colored resin composition contains an acrylic resin as the (A) resin, the heat treatment temperature is preferably 170°C or more, and the heat treatment time is preferably 30 minutes or more. Furthermore, regardless of the manufacturing conditions of the colored film, the size of the crystallites in the composition is the same as the size of the crystallites in the colored film produced from the composition. When the crystallite size of the imine pigment in the colored film is larger than 25 nm, the near-infrared transmittance decreases and the transmitted scattered light increases, so the clarity of the infrared camera image obtained through the colored film decreases. In addition, in the reflection tone, the diffuse reflectance (L* value in SCE) increases, so the darkness of the colored film decreases. In order to obtain a clearer infrared camera image and a jet-black reflective tone with better design, it is better to set the crystallite size of the imine pigment to 20 nm or less. On the other hand, when the crystallite size of the imine-based pigment in the colored film is less than 5 nm, the dispersion stability of the pigment is reduced, which may cause an increase in transmitted scattered light or visible light shading due to re-aggregation of the pigment. The issue of sexual decline. The crystallite size of the bisbenzofuranone-based pigment in the colored film is preferably 10 nm or more and 25 nm or less, and more preferably 10 nm or more and 20 nm or less, similarly to the methimine-based pigment. The crystallite size of other coloring materials is preferably as small as that of the methimine-based pigment and the bisbenzofuranone-based pigment, and the range is preferably 10 nm or more and 25 nm or less. Furthermore, when the crystallite size of the methimine-based pigment is α (nm) and the crystallite size of the bisbenzofuranone-based pigment is β (nm), by setting it to 3.0≦|α -β｜≦10.0, can improve the visible light shielding property without changing the reflectivity (L* in SCI). Generally speaking, in order to improve the visible light shielding property of the colored film, it is more effective to increase the content of the coloring material in the total solid content. However, in this case, there is a problem that the reflection tone of the colored film is reddish, and the design properties are deteriorated. , as a preferred aspect of the present invention, it is considered that by setting the difference in crystallite size between the imine-based pigment and the bisbenzofuranone-based pigment as described above, the filling properties of the coloring material can be improved and the visible light The shielding property is improved. As a means of setting the crystallite size of the pigment in the colored film to the above range, it is preferable to stably and uniformly disperse the pigment in a fine state without re-aggregation in the resin. More specifically, the following may be used: Methods of using pigments with smaller crystallite sizes; or methods of producing colored resin compositions by using the following bead mill method; etc.

As (B) the coloring material, the transmission tone and reflection tone of the coloring film can be adjusted by containing methimine-based pigments, bisbenzofuranone-based pigments, and other coloring materials within a range that does not inhibit the effects of the present invention. . In this case, it is preferable to contain a coloring material with a small crystallite size like the methimine-based pigment and the bisbenzofuranone-based pigment. Examples of coloring materials include commonly used organic pigments, inorganic pigments, dyes, and the like. In order to improve the heat resistance, reliability and light resistance of the colored film, organic pigments and inorganic pigments are preferred.

Examples of organic pigments include diketopyrrolopyrrole pigments; azo pigments such as azo, disazo, and polyazo; and phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, and metal-free phthalocyanine. Pigments; anthraquinone pigments such as diaminoanthraquinone, diaminoanthraquinone, anthrapyrimidine, flaxanthrone, anthrone, indanthrine, picanthrone, violetanthrone; quinacridone pigments ;two pigments; pyrenone pigments; perylene pigments; sulfur indigo pigments; isoindoline pigments; isoindolinone pigments; quinphthalone pigments; anthracene pigments; metal complex pigments, etc.

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

Examples of dyes include azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigo dyes, carbocation dyes, phthalocyanine dyes, methine dyes, polymethine dyes, and the like.

Examples of black organic pigments include carbon black, perylene black, and aniline black. Examples of mixed-color organic pigments include those in which two or more pigments having colors such as red, blue, green, purple, yellow, magenta, and cyan are mixed to form a pseudo-black color. 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, and nitrogen of the above metals. chemicals, nitrogen oxides, etc.

Examples of the white coloring material include titanium dioxide, barium carbonate, zirconium oxide, calcium carbonate, barium sulfate, aluminum white, silicon dioxide, and the like.

These coloring materials may contain two or more types.

Regarding the content of the (B) coloring material, it is important that the content of the (B) coloring material is 1 to 39 parts by weight relative to 100 parts by weight of the total content of solid components. Here, the (A) resin, (B) coloring material, and the following (D) photosensitive agent and (E) radically polymerizable compound contained in the solid component resin composition are included. Moreover, in the case where components other than these remain in the film when the colored film is formed, the components are also solid components. By setting the content of the coloring material (B) to 1 part by weight or more relative to 100 parts by weight of the total content of solid components, visible light shielding properties can be improved even in a thinner film. (B) The content of the coloring material is more preferably 10 parts by weight or more relative to 100 parts by weight of the total content of solid components. On the other hand, by setting the content of the coloring material (B) to 39 parts by weight or less with respect to 100 parts by weight of the total content of solid components, the reflection chromaticity of the colored film can be adjusted to be more achromatic. In addition, the reflection of incident light at the interface between the colored film and other base materials can be suppressed, thereby further improving the near-infrared transmittance. The upper limit of the content of the coloring material (B) relative to 100 parts by weight of the total solid content is preferably 35 parts by weight or less.

From the viewpoint of improving coatability, the colored resin composition of the present invention preferably contains (C) an organic solvent. (C) The organic solvent has the function of uniformly dissolving or dispersing (A) resin, (B) coloring material, etc. Furthermore, (C) the organic solvent is preferably a compound having a boiling point under atmospheric pressure of 110 to 250°C or less. Regarding the colored resin composition of the present invention, coating by printing methods such as spin coater, slit coater, screen printing, inkjet, gravure printing or rod coater is conceivable. Therefore, if the boiling point is less than At 110°C, the organic solvent dries faster and the coating uniformity is prone to abnormalities. On the other hand, if the boiling point exceeds 250° C., the organic solvent may remain in the obtained colored film, and the chemical resistance of the colored film may deteriorate.

Examples of (C) organic solvents include ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, alcohols, and the like.

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, and 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 Ether, tripropylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Examples of acetates include butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate. Ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, cyclohexanol acetate, propylene glycol Diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (hereinafter, "PGMEA"), dipropylene glycol methyl ether acetate, 3-methoxy-3-methyl-1-butan acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, etc. Examples of esters include lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate and 3-methoxypropionate. Methyl acid ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxyethyl acetate, ethyl glycolate, 2-hydroxy- Methyl 3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate Ester, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyl Isopropyl acid, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetyl acetate, ethyl acetyl acetate, ethyl 2-oxybutyrate, etc. Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like. Examples of aromatic hydrocarbons include toluene, xylene, and the like. Examples of amides include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and the like. Examples of alcohols include butanol, isobutanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, and 3-methyl-3-methoxybutanol. alcohol, diacetone alcohol, etc. These may contain 2 or more types.

Among these, in order to stabilize the dispersion of the coloring material, acetates are preferably used. When the weight of (C) organic solvent is 100 parts by weight, the content of acetate esters is preferably 40 to 100 parts by weight, more preferably 70 to 100 parts by weight.

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

The colored resin composition of the present invention contains an alkali-soluble resin as the (A) resin and further contains (D) a photosensitizer, whereby photosensitivity can be imparted. It can have a so-called negative photosensitivity, that is, the alkali solubility of the exposed part is reduced by pattern exposure through an exposure mask, and the unexposed part is removed by an alkaline developer to form a pattern; it can also have a so-called positive photosensitivity. The photosensitivity is achieved by pattern exposure through an exposure mask so that the alkali solubility of the exposed part is higher than that of the unexposed part, and the exposed part is removed by an alkaline developer to form the pattern. In the present invention, since it is easier to form a pattern with higher resolution even when the light shielding property is high, it is preferable to have negative photosensitivity.

By containing a photopolymerization initiator as the (D) photosensitizer and further containing the (E) radical polymerizable compound, negative photosensitivity can be imparted, that is, the exposed portion can be photocured by a radical polymerization reaction. (E) The radically polymerizable compound is preferably a compound having two or more radically polymerizable groups.

Photopolymerization initiator refers to a compound that generates free radicals due to bond breaking and/or reaction due to exposure. By containing a photopolymerization initiator, the (E) radically polymerizable compound can be photohardened by exposure.

Examples of the photopolymerization initiator include carbazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and α-aminoalkylphenone-based photopolymerization initiators. Polymerization initiator, etc. These may contain 2 or more types. Among them, in the following exposure step, the sensitivity to mixed rays including i rays (365 nm), h rays (405 nm), and g rays (436 nm) is higher, which is preferred. It is a carbazole-based photopolymerization initiator and an oxime ester-based photopolymerization initiator.

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

On the other hand, from the viewpoint of deep curability by exposure, the content of the photopolymerization initiator is preferably 60% by weight or less based on 100% by weight of the total content of the alkali-soluble resin and (E) radically polymerizable compound. , more preferably less than 40% by weight.

As the radical polymerizable group contained in (E) the radically polymerizable compound, from the viewpoint of improvement in sensitivity during exposure and improvement in hardness of the colored film, a (meth)acrylyl group is preferred. The "(meth)acrylyl group" referred to here means both the methacrylyl group and the acrylyl group.

From the viewpoint of improving the sensitivity to exposure, the content of the (E) radically polymerizable compound is preferably 5% by weight or more relative to the total content of the alkali-soluble resin and the (E) radically polymerizable compound, and more preferably 15% by weight or more. On the other hand, from the viewpoint of reflowability in the curing step, the content of the (E) radically polymerizable compound is preferably 80% by weight relative to the total content of the alkali-soluble resin and the (E) radically polymerizable compound. % or less, preferably 60% by weight or less.

By containing a photoacid generator as the (D) photosensitizer, the alkali solubility of the exposed part can be relatively improved and positive-type photosensitivity can be imparted.

As the photoacid generator, a quinonediazide compound is preferred. As the quinonediazide compound, an esterification product of a compound having a phenolic hydroxyl group and quinonediazide sulfonyl chloride is more preferred. In order to improve alkali solubility, part of the phenolic hydroxyl group may be deliberately left without esterification.

From the viewpoint of pattern processability, the content of the quinonediazide compound is preferably 1 to 50% by weight relative to the total amount of the alkali-soluble resin.

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

Polymer dispersants refer to those that have both a pigment-affinity group that chemically bonds or adsorbs to the pigment surface, and a polymer chain or group that has solvent affinity. Polymer dispersants exert the following effects in the following wet media dispersion processing, namely, improving the wettability of pigments to the dispersion medium, promoting the depolymerization of pigments, and improving the particle size and viscosity through steric hindrance and/or electrostatic repulsion effects. It is stable and thereby inhibits color separation of the colored resin composition during storage or coating.

Examples of the polymer dispersant include polyester-based polymer dispersants, acrylic-based polymer dispersants, polyurethane-based polymer dispersants, polyallylamine-based polymer dispersants, and carbodihydrides. Imine-based dispersants, polyamide-based polymer dispersants, etc. Among these, acrylic polymer dispersants and polyamide polymer dispersants are more preferred. As a polyamide-based polymer dispersant, one having a comb-like structure including several side chains of a polyester chain is preferred. More specifically, one having a main chain such as polyalkyleneimine is preferred. A compound that has a structure of multiple nitrogen atoms and has several side chains of the polyester chain that are amide bonded via the nitrogen atoms. Examples of polyamide-based dispersants with such a comb-like structure include "DISPERBYK" (registered trademark) 2200 (manufactured by BYK-Chemie Co., Ltd.), "SOLSPERSE" (registered trademark) 11200, and 28000 (both Lubrizol (stock) manufacturing), etc.

Polymer dispersants are classified into: dispersants with an amine value of 1 mgKOH/g or more and an acid value of less than 1 mgKOH/g, dispersants with an acid value of 1 mgKOH/g or more and an amine value of less than 1 mgKOH/g, amines Dispersants with a value of 1 mgKOH/g or more and an acid value of 1 mgKOH/g or more, dispersants with an amine value of less than 1 mgKOH/g and an acid value of less than 1 mgKOH/g. These may contain 2 or more types. Among these, a dispersant with an amine value of 1 mgKOH/g or more is preferred.

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, 9077; "BYK" (registered trademark)-LPN6919, "DISPERBYK"-LPN21116, "DISPERBYK"-LPN21234 (the above are all manufactured by BYK-Chemie) ; "EFKA" (registered trademark) 4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403, 4800 (the above are all manufactured by BASF); " "Ajisper" (registered trademark) PB711 (manufactured by Ajinomoto Fine-Techno Co., Ltd.); "SOLSPERSE" 13240, 13940, 20000, 71000, 76500 (the above are all manufactured by Lubrizol Co., Ltd.), etc.

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, Anti-Terra- 205 (the above, all manufactured by BYK-Chemie); "SOLSPERSE" 24000 (manufactured by Lubrizol Co., Ltd.); "Ajisper" PB821, PB880, PB881 (the above, all manufactured by Ajinomoto Fine-Techno Co., Ltd.); " SOLSPERSE" 9000, 11200, 13650, 24000SC, 24000GR, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 39000, 56000 (manufactured by Lubrizol Co., Ltd.), etc.

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

The colored resin composition of the present invention may also contain a thermal crosslinking agent. By containing a thermal cross-linking agent, the strength of the final coating film can be improved. Examples of thermal cross-linking agents include: melamine-based cross-linking agents, Oxazoline-based cross-linking agents, carbodiimide-based cross-linking agents, isocyanate-based cross-linking agents, aziridine-based cross-linking agents, epoxy-based cross-linking agents, etc. These may contain 2 or more types.

The colored resin composition of the present invention may also contain a leveling agent. By containing a leveling agent, the coating properties or the surface smoothness of the colored film can be improved. Examples of leveling agents include: anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine; and cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride. ; Lauryl dimethyl amine oxide, lauryl carboxymethyl hydroxyethylimidazolium betaine and other amphoteric surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitol monostearate, etc. Nonionic surfactants; silicone surfactants with polydimethylsiloxane as the main skeleton; fluorine surfactants, etc. These may contain 2 or more types. Examples of commercially available surfactants include "BYK"-302, "BYK"-333, "BYK"-3550, and "BYK"-392 (all of the above are manufactured by BYK-Chemie).

Regarding the colored resin composition of the present invention, when the colored film is formed so that the optical density (OD value) becomes 4, the average light transmittance of the colored film in the near-infrared region with a wavelength of 920 nm to 960 nm is preferably 90%. Above, preferably above 95%. If the average light transmittance in the wavelength range of 920 nm to 960 nm is above 90%, the infrared intensity obtained through the colored film can be further improved, and the near-infrared sensor sensitivity or near-infrared camera image illumination can be further improved.

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

Regarding the light transmittance of the colored film, a coated film of the colored resin composition can be formed on a transparent base material. After drying the coated film with a heating plate or the like, the colored film can be obtained by heating it with a hot air oven or the like. The light transmittance of the material is used as a reference and measured using a UV-visible near-infrared spectrophotometer. As described above, the colored film is preferably one in which the crosslinkable group contained in the resin (A) in the colored resin composition is crosslinked by heat and/or light and does not substantially remain. For example, in the colored resin composition, it is preferable that When an acrylic resin is used as the resin (A), the heat treatment temperature is preferably 170°C or more, and the heat treatment time is preferably 30 minutes or more. As the ultraviolet-visible light spectrophotometer, UV-3150 (manufactured by Shimadzu Corporation) is preferred, and as the transparent substrate, TEMPAX (manufactured by AGC Techno Glass Co., Ltd.) which is a translucent glass substrate is preferred. Furthermore, regarding the OD value of the coating or colored film, an optical density meter (361TVisual; manufactured by X-Rite Co., Ltd.) can be used to measure the intensity of incident light and transmitted light of the coating or colored film respectively, and use the following formula (3) Calculate the OD value of the coating or colored film. OD value = log ₁₀ (I ₀ /I)・・・Equation (3) I ₀ : incident light intensity I : transmitted light intensity.

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

Regarding the colored resin composition of the present invention, a colored film is formed on alkali-free glass with a thickness of 0.7 mm so that the OD value becomes 4, and CIE1976 (L*, a*, b* measured from the glass surface by the SCI method ) Reflection chromaticity values (a*, b*) in the colorimetric system are preferably -0.5≦a ^* ≦1.0 and -1.0≦b ^* ≦0.5, and more preferably 0.0≦a ^* ≦1.0 and -1.0≦b ^* ≦0.0. The reflection chromaticity becomes an index of the hue of the image reflected in the colored film. In the SCI method, the closer it is to (a*, b*) = (0.0, 0.0), the more it can be called an achromatic reflection hue. On the other hand, regarding the reflection tone of a liquid crystal display device or an organic electroluminescence (EL, Electroluminescence) display when it is not lit, generally speaking, b* in the SCI method is a negative value and has a blue tone, so the display device The decorative film used in the film is preferably a negative value of b*. The reflection colorimetric value (L*) in the CIE1976 (L*, a*, b*) colorimetric system obtained by measuring the colored film formed in the same way by SCE from the glass surface is preferably L*. ≦3.0, preferably L*≦2.0. (L*) in the SCI method is an indicator of diffuse reflectance. The closer it is to (L*) = (0.0), the more it can be called a dark reflective tone. From a design perspective, it is better to be dark. Reflective tones.

The colorimetric value (color value) obtained by using a colorimeter is greatly affected by the lighting and light-receiving geometric conditions. The geometric conditions of the colorimeter are roughly divided into 45-degree illumination system and diffuse illumination system using integrating sphere. Diffuse lighting systems are further divided into Specular Component Included (SCI, Specular Component Included) and Specular Component Excluded (SCE, Specular Component Excluded) based on the different processing methods of specular reflection components using light traps. In SCI, all specular reflection components produced by the sample are integrated. On the other hand, in SCE, the specular reflection component is removed by a light trap provided on the wall surface of the integrating sphere, so the diffuse reflection component is measured.

The reflection chromaticity (L*, a*, b*) of the colored film can be obtained by using a spectrum corrected with a white correction plate (CM-A145; manufactured by Konica Minolta Co., Ltd.) Colorimeter (CM-2600d; manufactured by Konica Minolta Co., Ltd.), measuring self-transparency under the measurement conditions of standard light source D65 (color temperature 6504 K), viewing angle 2° (CIE1976), atmospheric pressure, and 20°C Total reflection chromaticity (SCI) and diffuse reflection chromaticity (SCE) of light incident on the substrate.

As a method for producing the colored resin composition of the present invention, for example, a method of dispersing a resin solution containing (A) resin, (B) coloring material, and (C) organic solvent using a dispersing machine and preparing it in advance is preferable. This is a method of adding (A) resin, photosensitizer and other other ingredients as necessary to a coloring material dispersion with a high coloring material concentration and stirring it. You can also filter if necessary.

In the present invention, it is preferable to use a pigment that has been micronized in advance as the coloring material (B). Examples of means for micronizing pigments include: salt milling, which involves kneading and grinding pigments, inorganic salts, and organic solvents; or acidic slurry, which involves temporarily dissolving the pigment in a strong acid such as sulfuric acid and mixing it with a poor solvent. ;wait.

The salt grinding treatment is preferably a method of kneading a pigment, a water-soluble inorganic salt, and an organic solvent that does not dissolve the inorganic salt, then pouring the kneaded product into water, and filtering and washing the obtained slurry. Methods to remove inorganic salts. Resins or pigment derivatives such as polymer dispersants can also be added together with pigments, water-soluble inorganic salts and organic solvents to inhibit the re-aggregation of pigments after micronization by salt milling.

Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, calcium chloride, barium chloride, sodium sulfate, and the like.

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, the organic solvent is easily evaporated, so in terms of safety, it is preferred. It is a high boiling point solvent. Examples include: 2-methoxyethanol, 2-butoxyethanol, 2-(isoamyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, and diethylene glycol monomethyl ether. , diethylene glycol monoethylene 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, low molecular weight polypropylene glycol, etc. Two or more types of these may be used.

Examples of kneading devices include kneaders, kneaders, planetary mixers such as "Trimix" (registered trademark) manufactured by Inoue Manufacturing Co., Ltd., and continuous single-shaft kneaders manufactured by Asada Iron Works Co., Ltd. Manufactured by "Miracle KCK" (registered trademark), etc.

Examples of a dispersing machine for dispersing a resin solution containing (A) resin, (B) coloring material, and (C) organic solvent include: ball mill, bead mill, sand mill, three-roller mill, high-speed Impact grinder etc. Among these, a bead mill is preferred for dispersion efficiency and fine dispersion. Examples of the bead mill include a coball mill, a basket mill, a pin mill, and a horizontal dispersion disk mill (Dyno Mill). Examples of beads in a bead mill include titanium oxide beads, zirconia beads, and zircon beads.

In the present invention, it is preferable to carry out dispersion in multiple stages by a bead mill, and it is preferable to have the following steps, that is, by using an average bead particle size greater than 0.1 mm After the beads are dispersed in a bead mill, the average bead diameter is 0.1 mm. The following steps are used to disperse the beads in a bead mill. By using average bead diameter greater than 0.1 mm The beads are dispersed in a bead mill, which can effectively crush pigments with larger crystallite sizes. Subsequently, by using an average bead size of 0.1 mm The following micro-beads are dispersed using a bead mill, thereby reducing the energy imparted to the pigment. While maintaining the surface activity of the pigment, micro-dispersion can be performed to suppress the re-aggregation of the pigment in the colored resin composition. to spread it more evenly. In this case, it is preferable that the bead mill is equipped with a centrifugal separation separator that can separate the fine beads and the dispersion liquid. Here, the average bead diameter refers to the numerical average of the circular equivalent diameters of the beads. Specifically, the bead diameter can be obtained as follows: using a stereomicroscope to magnify the beads to 45 times for photography, measure the longest diameter and shortest diameter of 100 randomly selected beads, and compare them. The average value is set as the circle equivalent diameter, and the numerical average value is calculated.

A colored film can be obtained by forming the colored resin composition of the present invention into a film shape. Specifically, the colored resin composition of the present invention is coated on a transparent substrate such as glass, plastic, film, etc., and when an organic solvent is included, the organic solvent is dried and distilled away, and a hardening reaction is performed if necessary. This results in a tinted film. The coating method is not particularly limited. Depending on the liquid characteristics of the base material and the colored resin composition, examples include: screen printing, offset printing, pad printing, letterpress printing, gravure printing, inkjet printing, gravure coating, roller Coating, reverse roller coating, roller blade coating, rod coating, curtain flow coating, die nozzle coating, spin coating, air knife coating, spray coating, etc.

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

The photosensitive colored resin composition is coated on the 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 rotator, spray coating, inkjet coating, die coating, roller coating, and the like. The film thickness of the coating film can be appropriately selected depending on the coating method, etc. Generally speaking, the film thickness after drying is set to 1 to 150 μm.

The obtained coating film is dried to obtain a dry film. Examples of drying methods include heat drying, air drying, reduced pressure drying, infrared irradiation, and the like. Examples of the heating and drying device include an oven, a heating plate, and the like. The drying temperature is preferably 50°C to 150°C, and the drying time is preferably 1 minute to several hours.

The obtained dry film is irradiated with actinic rays through a mask having the desired pattern to obtain an exposed film. Examples of the actinic rays to be irradiated include ultraviolet rays, visible rays, electron beams, X-rays, and the like. It is preferable to irradiate the colored resin composition of the present invention with i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of a mercury lamp.

The obtained exposed film is developed using an alkaline developer or the like to remove unexposed portions and obtain a pattern. Examples of the alkaline compound used in the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and ammonia; ethylamine, Primary amines such as n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; tetramethylammonium hydroxide (TMAH) and other tertiary amines Alkyl ammonium hydroxides, choline and other quaternary ammonium salts; triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol and other alcoholamines; pyrrole, piperidine, 1,8-bis Azabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane, Organic bases such as cyclic amines such as phosphonines.

The concentration of the alkaline compound in the alkaline developer is usually 0.01 to 50% by weight, preferably 0.02 to 3% by weight. In addition, in order to improve the pattern shape after development, 0.1 to 5% by weight of nonionic surfactants and other surfactants may be added. Furthermore, when the developer is an alkali aqueous solution, water-soluble organic solvents such as ethanol, γ-butyrolactone, dimethylformamide, and N-methyl-2-pyrrolidone may be added to the developer.

Examples of the development method include a dipping method, a spray method, a liquid coating method, and the like. You can also use pure water to rinse the obtained pattern.

By subjecting the obtained pattern to heat treatment (post-baking), a patterned colored film can be obtained. The heat treatment can be performed in air, in a nitrogen atmosphere, or in a vacuum state. The heating temperature is preferably 150 to 300°C, and the heating time is preferably 0.25 to 5 hours. The heating temperature can be changed continuously or in stages.

The colored resin composition and colored film of the present invention have high light-shielding properties in the visible light region, high transmittance in the near-infrared region, and the reflection and transmission hues are achromatic, so they are suitable for use in smart phones or Colored film for decorative substrates in display terminals such as tablet personal computers (PCs), near-infrared sensors for driver monitoring or gesture sensors in vehicle monitors or vehicle instruments, and decorative panels for near-infrared camera concealment Colored films, decorative films and resin molded products for concealing LiDAR sensors, colored films for icons in vehicle displays or vehicle instruments, light-shielding images such as black matrices of color filters included in liquid crystal display devices, etc., and interiors of organic EL displays Colored partition walls, etc.

The decorative substrate of the present invention refers to a substrate provided with a substrate as a support for a colored film and the colored film of the present invention. Decoration (including the case of a single color) is realized by the colored film of the present invention. Examples of decorative substrates include cover glass substrates for smartphones, tablet PCs, in-vehicle displays, etc., or housing lens substrates for concealing near-infrared cameras or near-infrared sensors. [Example]

Hereinafter, the present invention will be described in detail with reference to specific examples, but the present invention is not limited to the examples given here.

＜Evaluation method＞ [Pigment crystallite size] The colored resin composition was coated on an alkali-free glass substrate (AN100) with a thickness of 0.7 mm using a spinner (1H-DS) manufactured by Mikasa Co., Ltd., and the coating film was heated on a 100°C hot plate for 2 minutes. dry. The dried film was baked in a hot air oven at 230° C. for 30 minutes to obtain a colored film. The obtained colored film was cut off from the glass plate and placed in an aluminum standard sample holder. An X-ray diffraction device DS ADVANCE (trade name) manufactured by Bruker AXS Co., Ltd. was used, and the X-ray source was CuKα ray, and the X-ray diffraction spectrum was measured by the wide-angle X-ray diffraction method. As measurement conditions, the output is 40 kV/40 mA, the slit system is Div. Slit: 0.3°, the measurement step distance (2θ) is 0.0171°, and the measurement time is 0.5 seconds/step. The diffraction angle and half-maximum width of the obtained main peak were measured, and the crystallite size was determined using Scherrer's formula represented by the above formula (1).

The methimine pigment Bk-1 described in Production Example 1 has the strongest main peak observed at a diffraction angle 2θ=26.25° or more and 26.45° or less. The bisbenzofuranone pigment Bk described in Production Example 2 -2 is the main peak with the strongest intensity observed when the diffraction angle 2θ=7.80° or more and 8.00° or less.

[Light-shielding property] For the colored film, an optical density meter 361TVisual manufactured by X-Rite Corporation was used to calculate the OD value per 1 μm of film thickness.

[Visible light transmittance chromaticity and near-infrared transmittance] For the colored film formed by adjusting the OD value to 1.0, the transmittance in the wavelength range of 380 nm to 780 nm was measured using a UV-visible spectrophotometer UV-3150 manufactured by Shimadzu Corporation, and the transmission chromaticity ( x, y). In addition, for the colored film formed by adjusting the OD value to 4.0, the transmittance at wavelengths from 920 nm to 960 nm was measured in the same manner to determine the average transmittance. The higher the average transmittance, the better the light transmittance in the near-infrared region. In addition, the transmittance shown in the table only represents the value of the colored film, and the transmittance is measured using the substrate as a reference.

[Near-infrared camera image] Regarding the colored film, an infrared camera module Freemo manufactured by Alpha Technology was placed on the back side of the colored film, and the obtained camera image was evaluated based on the following criteria. A: A clear image can be confirmed B: Although the image can be confirmed, the outline is not clear. C: The image cannot be confirmed.

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

(Synthesis Example 1 Synthesis of Acrylic Resin (P-1)) By the method described in Example 1 of Japanese Patent No. 3120476, a methyl methacrylate/methacrylic acid/styrene copolymer (weight ratio 30/40/30) was synthesized. To 100 parts by weight of the obtained copolymer, 40 parts by weight of glycidyl methacrylate was added, reprecipitated with purified water, filtered and dried to obtain a weight average molecular weight of 15,000 and an acid value of 110 mgKOH/g. Acrylic resin (P-1). Furthermore, the acid value of the acrylic resin is set as the amount of potassium hydroxide (mg) required to neutralize 1 g of acrylic resin (unit: mgKOH/g), and the weight average molecular weight is determined by gel permeation chromatography (GPC). "HLC-8220GPC" (a test device manufactured by Tosot Co., Ltd.) uses tetrahydrofuran as the carrier and measures it in polystyrene conversion.

(Manufacture Example 1: Production of methimine pigment Bk-1) Chromofine Black A1103 manufactured by Daiinichi Seika Co., Ltd., which is a formimine-based pigment, 2400 g of sodium chloride, and 400 g of diethylene glycol were put into a kneader (manufactured by Moriyama Seisakusho Co., Ltd., S-type kneading) machine (trade name)) and knead at 70°C for 8 hours. Next, the kneaded product is put into about 10 L of warm water, heated to 40°C, and stirred with a high-speed mixer for 1 hour to form a slurry. Thereafter, it is filtered and washed with water to remove sodium chloride and diamine. Ethylene glycol and vacuum drying at 80°C for 24 hours to obtain the imine pigment Bk-1.

(Production Example 2: Production of bisbenzofuran-based pigment Bk-2) "Irgaphor" Black S0100CF manufactured by BASF Co., Ltd., which is a dibenzofuran-based pigment, 2400 g of sodium chloride, and 400 g of diethylene glycol were put into a kneader (manufactured by Moriyama Seisakusho Co., Ltd., S-type kneading) machine (trade name)) and knead at 70°C for 8 hours. Next, the kneaded product is put into about 10 L of warm water, heated to 40°C, and stirred with a high-speed mixer for 1 hour to form a slurry. Thereafter, it is filtered and washed with water to remove sodium chloride and diamine. Ethylene glycol and vacuum drying at 80°C for 24 hours to obtain bisbenzofuran pigment Bk-2.

(Production Example 3: Production of blue pigment PB15:6-1) Put 200 g of "LIONOL BLUE ES" (PB15: 6) manufactured by Toyocolor Co., Ltd., 2400 g of sodium chloride and 400 g of diethylene glycol into a kneader (manufactured by Moriyama Seisakusho Co., Ltd., S-type kneading machine (trade name)) and knead at 70°C for 8 hours. Next, the kneaded product is put into about 10 L of warm water, heated to 40°C, and stirred with a high-speed mixer for 1 hour to form a slurry. Thereafter, it is filtered and washed with water to remove sodium chloride and diamine. Ethylene glycol and vacuum drying at 80°C for 24 hours to obtain blue pigment PB15:6-1.

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

(Production Example 5: Production of yellow pigment PY150-1) Yellow pigment PY150 was obtained in the same manner as in Production Example 3, except that "E-4GN" (PY150) manufactured by Lanxess Co., Ltd. was used instead of "LIONOL BLUE ES" (PB15: 6) manufactured by Toyocolor Co., Ltd. -1.

(Manufacture Example 6: Production of Coloring Material Dispersion Liquid (D-1)) Propylene glycol monomethyl ether acetic acid of 120 g of methimine pigment Bk-1, acrylic resin (P-1) obtained by Synthesis Example 1 Add 171 g of 35% by weight ester (PGMEA) solution, 20 g of polyamide-based polymer dispersant "DISPERBYK" 2200 (BYK-2200) as a polymer dispersant, and 689 g of PGMEA into the tank, and stir with a homogeneous mixer. 20 minutes to obtain a preliminary dispersion. Filled with beads diameter 0.30 mm The obtained preliminary dispersion liquid was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Industry Co., Ltd. equipped with a centrifugal separation separator containing 75% by volume of zirconia beads, and dispersed for 20 minutes at a rotation speed of 12 m/s. Then, the liquid after the dispersion treatment was supplied to a container filled with beads with a diameter of 0.05 mm. 75% by volume of zirconia beads in Ultra Apex Mill UAM015, dispersed for 90 minutes at a rotation speed of 8 m/s to obtain a solid content concentration of 20% by weight, coloring material/(resin + dispersant) (weight ratio) = 60/40 coloring material dispersion D-1.

(Manufacture Example 7: Production of Coloring Material Dispersion Liquid (D-2)) Propylene glycol monomethyl ether acetic acid of 120 g of methimine pigment Bk-1, acrylic resin (P-1) obtained by Synthesis Example 1 Add 171 g of 35% by weight ester (PGMEA) solution, 20 g of polyamide-based polymer dispersant "DISPERBYK" 2200 (BYK-2200) as a polymer dispersant, and 689 g of PGMEA into the tank, and stir with a homogeneous mixer. 20 minutes to obtain a preliminary dispersion. Use bead size 1.00 mm The zirconia beads were dispersed for 3 hours with a paint shaker (Toyo Seiki Manufacturing Co., Ltd.), and then filtered through a 5 μm filter to obtain a solid content concentration of 20% by weight, coloring material/(resin + high Molecular dispersant) (weight ratio) = 60/40 coloring material dispersion D-2.

(Production Example 8: Production of Coloring Material Dispersion Liquid (D-3)) A solid content concentration of 20% by weight and a coloring material/(resin + dispersant) were obtained in the same manner as in Production Example 6 except that bisbenzofuran-based pigment Bk-2 was used instead of methimine-based pigment Bk-1. Coloring material dispersion D-3 (weight ratio)=60/40.

(Production Example 9: Production of Coloring Material Dispersion Liquid (D-4)) A solid content concentration of 20% by weight and a coloring material/(resin + dispersant) were obtained in the same manner as in Production Example 7 except that bisbenzofuran-based pigment Bk-2 was used instead of methimine-based pigment Bk-1. Coloring material dispersion D-4 (weight ratio)=60/40.

(Production Example 10: Production of Coloring Material Dispersion Liquid (D-5)) Propylene glycol monomethyl ether of 120 g of the above-mentioned blue pigment PB15:6-1 and the acrylic resin (P-1) obtained by Synthesis Example 1 171 g of a 35% by weight acid ester (PGMEA) solution, 20 g of an amine-based polymer dispersant "BYK LPN-21116" as a polymer dispersant, and 689 g of PGMEA were added to the tank and stirred for 20 minutes with a homogeneous mixer to obtain Prepare the dispersion. Filled with beads diameter 0.50 mm The obtained preliminary dispersion liquid was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Industry Co., Ltd. equipped with a centrifugal separation separator containing 75% by volume of zirconia beads, and dispersed for 20 minutes at a rotation speed of 12 m/s. Then, the liquid after the dispersion treatment was supplied to a container filled with beads with a diameter of 0.05 mm. 75% by volume of zirconia beads in Ultra Apex Mill UAM015, dispersed for 90 minutes at a rotation speed of 8 m/s to obtain a solid content concentration of 20% by weight, coloring material/(resin + polymer dispersant) (weight ratio )=60/40 coloring material dispersion D-5.

(Production Example 11: Production of Coloring Material Dispersion Liquid (D-6)) Except using red pigment PR177-1 instead of blue pigment PB15:6-1, the solid content concentration of 20% by weight and coloring material/(resin + dispersant) (weight ratio) were obtained in the same manner as in Production Example 10. =60/40 coloring material dispersion D-6.

(Production Example 12: Production of Coloring Material Dispersion Liquid (D-7)) Except using the yellow pigment PY150-1 instead of the blue pigment PB15:6-1, the solid content concentration of 20% by weight and the coloring material/(resin + dispersant) (weight ratio) were obtained in the same manner as in Production Example 10. =60/40 coloring material dispersion D-7.

(Production Example 13: Production of coloring material dispersion liquid (D-8)) Propylene glycol monomethyl ether acetic acid of 120 g of methimine pigment Bk-1, acrylic resin (P-1) obtained by synthesis example 1 Add 171 g of 35% by weight ester (PGMEA) solution, 20 g of polyamide-based polymer dispersant "DISPERBYK" 2200 (BYK-2200) as a polymer dispersant, and 689 g of PGMEA into the tank, and stir with a homogeneous mixer. 20 minutes to obtain a preliminary dispersion. Filled with beads diameter 0.30 mm The obtained preliminary dispersion liquid was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Industry Co., Ltd. equipped with a centrifugal separation separator containing 75% by volume of zirconia beads, and dispersed for 20 minutes at a rotation speed of 12 m/s. Then, the liquid after the dispersion treatment was supplied to a container filled with beads with a diameter of 0.10 mm. 75% by volume of zirconia beads in Ultra Apex Mill UAM015, dispersed for 90 minutes at a rotation speed of 8 m/s to obtain a solid content concentration of 20% by weight, coloring material/(resin + dispersant) (weight ratio) = 60/40 coloring material dispersion D-8.

(Manufacture Example 14: Production of Coloring Material Dispersion Liquid (D-9)) Propylene glycol monomethyl ether acetic acid of 120 g of methimine pigment Bk-1 and acrylic resin (P-1) obtained by Synthesis Example 1 Add 171 g of 35% by weight ester (PGMEA) solution, 20 g of polyamide-based polymer dispersant "DISPERBYK" 2200 (BYK-2200) as a polymer dispersant, and 689 g of PGMEA into the tank, and stir with a homogeneous mixer. 20 minutes to obtain a preliminary dispersion. Filled with beads diameter 0.30 mm The obtained preliminary dispersion liquid was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Industry Co., Ltd. equipped with a centrifugal separation separator containing 75% by volume of zirconia beads, and dispersed for 20 minutes at a rotation speed of 12 m/s. Then, the liquid after the dispersion treatment was supplied to a container filled with beads with a diameter of 0.03 mm. 75% by volume of zirconia beads in Ultra Apex Mill UAM015, dispersed for 90 minutes at a rotation speed of 8 m/s to obtain a solid content concentration of 20% by weight, coloring material/(resin + dispersant) (weight ratio) = 60/40 coloring material dispersion D-9.

(Production Example 15: Production of Coloring Material Dispersion Liquid (D-10)) A solid content concentration of 20% by weight and a coloring material/(resin + dispersant) were obtained in the same manner as in Production Example 14 except that bisbenzofuran-based pigment Bk-2 was used instead of methimine-based pigment Bk-1. Coloring material dispersion D-10 (weight ratio) = 60/40.

(Production Example 16: Production of Coloring Material Dispersion Liquid (D-11)) Propylene glycol monomethyl ether of 120 g of bisbenzofuran pigment Bk-2 and the acrylic resin (P-1) obtained in Synthesis Example 1 Add 171 g of a 35% by weight acid ester (PGMEA) solution, 20 g of the polyamide-based polymer dispersant "DISPERBYK" 2200 (BYK-2200) as a polymer dispersant, and 689 g of PGMEA into the tank, and use a homogeneous mixer Stir for 20 minutes to obtain a preliminary dispersion liquid. Filled with beads diameter 0.30 mm The obtained preliminary dispersion liquid was supplied to a dispersing machine Ultra Apex Mill UAM015 manufactured by Kotobuki Industry Co., Ltd. equipped with a centrifugal separation separator containing 75% by volume of zirconia beads, and dispersed for 20 minutes at a rotation speed of 12 m/s. Then, the liquid after the dispersion treatment was supplied to a container filled with beads with a diameter of 0.02 mm. 75% by volume of zirconia beads in Ultra Apex Mill UAM015, dispersed for 90 minutes at a rotation speed of 8 m/s to obtain a solid content concentration of 20% by weight, coloring material/(resin + dispersant) (weight ratio) = 60/40 coloring material dispersion D-11.

Table 1 shows the composition and dispersion conditions of the coloring material dispersions of Production Examples 6 to 16.

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

(Example 1) To a mixture of 21.67 g of the coloring material dispersion (D-1) and 5.42 g of the coloring material dispersion (D-3), 31.04 g of a 35% by weight PGMEA solution of the acrylic polymer (P-1), 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 silicone-based surfactant A solution obtained by dissolving 0.30 g of a 10% by weight PGMEA solution of surfactant "BYK" 333 (manufactured by BYK-Chemie) in 32.90 g of PGMEA to obtain a total solids concentration of 25% by weight, relative to 100% of the total solids. The content of the coloring material is 13 parts by weight of the coloring resin composition PC-1.

The obtained colored resin composition PC-1 was coated on an alkali-free glass substrate (AN100) with a thickness of 0.7 mm using a spinner (1H-DS) manufactured by Mikasa Co., Ltd., and the coating was performed on a hot plate at 100°C. The film was heated and dried for 2 minutes. The dried film was post-baked at 230° C. for 30 minutes in a hot air oven to obtain colored film C-1. Table 2 shows the results of evaluating the colored film C-1 by the above method.

(Example 2) Colored resin composition PC-2 was obtained in the same manner as in Example 1 except that the coloring material dispersion liquid (D-1) was 20.31 g and the coloring material dispersion liquid (D-3) was 6.77 g. . Using the obtained colored resin composition PC-2, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 3) Colored resin composition PC-3 was obtained in the same manner as in Example 1 except that the coloring material dispersion liquid (D-1) was 13.54 g and the coloring material dispersion liquid (D-3) was 13.54 g. . Using the obtained colored resin composition PC-3, the same evaluation as in Example 1 was performed. The results are shown in Table 2. Moreover, the X-ray diffraction spectrum of the obtained colored film is shown in FIG. 1 .

(Example 4) Colored resin composition PC-4 was obtained in the same manner as in Example 1 except that the coloring material dispersion liquid (D-1) was 9.48 g and the coloring material dispersion liquid (D-3) was 17.60 g. . Using the obtained colored resin composition PC-4, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 5) Colored resin composition PC-5 was obtained in the same manner as in Example 1 except that the coloring material dispersion liquid (D-1) was 6.77 g and the coloring material dispersion liquid (D-3) was 20.31 g. . Using the obtained colored resin composition PC-5, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 6) To the mixed liquid of 41.67 g of the coloring material dispersion liquid (D-1) and 10.42 g of the coloring material dispersion liquid (D-3), 20.73 g of a 35% by weight PGMEA solution of the acrylic polymer (P-1), 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 silicone-based surfactant as a surfactant A solution obtained by dissolving 0.30 g of a 10% by weight PGMEA solution of "BYK" 333 (manufactured by BYK-Chemie) in 19.59 g of PGMEA to obtain a total solids concentration of 25% by weight, relative to 100 parts by weight of the total solids. The content of the coloring material is 25 parts by weight of the coloring resin composition PC-6. Using the obtained colored resin composition PC-6, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 7) Colored resin composition PC-7 was obtained in the same manner as in Example 6 except that the coloring material dispersion liquid (D-1) was 39.06 g and the coloring material dispersion liquid (D-3) was 13.02 g. . Using the obtained colored resin composition PC-7, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 8) Colored resin composition PC-8 was obtained in the same manner as in Example 6 except that the coloring material dispersion liquid (D-1) was 26.04 g and the coloring material dispersion liquid (D-3) was 26.04 g. . Using the obtained colored resin composition PC-8, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 9) Colored resin composition PC-9 was obtained in the same manner as in Example 6 except that the coloring material dispersion liquid (D-1) was 18.23 g and the coloring material dispersion liquid (D-3) was 33.85 g. . Using the obtained colored resin composition PC-9, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 10) Colored resin composition PC-10 was obtained in the same manner as in Example 4 except that the coloring material dispersion liquid (D-1) was 13.02 g and the coloring material dispersion liquid (D-3) was 39.06 g. . Using the obtained colored resin composition PC-10, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 11) To a mixture of 10.00 g of the coloring material dispersion (D-1) and 2.50 g of the coloring material dispersion (D-3), 37.02 g of a 35% by weight PGMEA solution of the acrylic polymer (P-1), 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 silicone-based surfactant as a surfactant A solution obtained by dissolving 0.30 g of a 10% by weight PGMEA solution of "BYK" 333 (manufactured by BYK-Chemie) in 40.67 g of PGMEA to obtain a total solids concentration of 25% by weight, relative to 100 parts by weight of the total solids. The content of the coloring material is 6 parts by weight of the coloring resin composition PC-11. Using the obtained colored resin composition PC-11, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 12) Colored resin composition PC-12 was obtained in the same manner as in Example 11 except that the coloring material dispersion liquid (D-1) was 9.38 g and the coloring material dispersion liquid (D-3) was 3.13 g. . Using the obtained colored resin composition PC-12, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 13) Colored resin composition PC-13 was obtained in the same manner as in Example 11 except that the coloring material dispersion liquid (D-1) was 6.25 g and the coloring material dispersion liquid (D-3) was 6.25 g. . Using the obtained colored resin composition PC-13, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 14) Colored resin composition PC-14 was obtained in the same manner as in Example 11 except that the coloring material dispersion liquid (D-1) was 4.38 g and the coloring material dispersion liquid (D-3) was 8.13 g. . Using the obtained colored resin composition PC-14, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 15) Colored resin composition PC-15 was obtained in the same manner as in Example 11 except that the coloring material dispersion liquid (D-1) was 3.13 g and the coloring material dispersion liquid (D-3) was 9.38 g. . Using the obtained colored resin composition PC-15, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 16) To a mixture of 31.25 g of coloring material dispersion (D-1) and 31.25 g of coloring material dispersion (D-3), 16.45 g of a 35% by weight PGMEA solution of acrylic polymer (P-1), 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 silicone-based surfactant as a surfactant A solution obtained by dissolving 0.30 g of a 10% by weight PGMEA solution of "BYK" 333 (manufactured by BYK-Chemie) in 14.04 g of PGMEA to obtain a total solids concentration of 25% by weight, relative to 100 parts by weight of the total solids. The content of the coloring material is 30 parts by weight of the coloring resin composition PC-16. Using the obtained colored resin composition PC-16, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 17) To the mixed liquid of 36.46 g of the coloring material dispersion liquid (D-1) and 36.46 g of the coloring material dispersion liquid (D-3), 12.16 g of a 35% by weight PGMEA solution of the acrylic polymer (P-1), 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 silicone-based surfactant as a surfactant A solution obtained by dissolving 0.30 g of a 10% by weight PGMEA solution of "BYK" 333 (manufactured by BYK-Chemie) in 8.49 g of PGMEA to obtain a total solids concentration of 25% by weight, relative to 100 parts by weight of the total solids. The content of the coloring material is 35 parts by weight of the coloring resin composition PC-17. Using the obtained colored resin composition PC-17, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 18) To the mixed liquid of 40.63 g of the coloring material dispersion liquid (D-1) and 40.63 g of the coloring material dispersion liquid (D-3), 8.73 g of a 35% by weight PGMEA solution of the acrylic polymer (P-1), 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 silicone-based surfactant as a surfactant A solution obtained by dissolving 0.30 g of a 10% by weight PGMEA solution of "BYK" 333 (manufactured by BYK-Chemie) in 4.05 g of PGMEA to obtain a total solids concentration of 25% by weight, relative to 100 parts by weight of the total solids. The content of the coloring material is 35 parts by weight of the coloring resin composition PC-18. Using the obtained colored resin composition PC-18, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 19) Colored resin composition PC-19 was obtained in the same manner as in Example 3, except that the coloring material dispersion liquid (D-2) was used instead of the coloring material dispersion liquid (D-1). Using the obtained colored resin composition PC-19, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 20) Colored resin composition PC-20 was obtained in the same manner as in Example 3, except that the coloring material dispersion liquid (D-4) was used instead of the coloring material dispersion liquid (D-3). Using the obtained colored resin composition PC-20, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 21) To a mixture of 12.19 g of coloring material dispersion liquid (D-1), 12.19 g of coloring material dispersion liquid (D-3), and 2.71 g of coloring material dispersion liquid (D-5), add acrylic polymer ( 31.02 g of PGMEA 35% by weight solution of P-1), 8.32 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a multifunctional monomer, and KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver A solution obtained by dissolving 0.38 g of a 10% by weight PGMEA solution of the silicone surfactant "BYK" 333 (manufactured by BYK-Chemie) as a surfactant in 32.90 g of PGMEA to obtain a total solid concentration of The coloring resin composition PC-21 contains 25% by weight and 13 parts by weight of the coloring material relative to 100 parts by weight of the total solid content. Using the obtained colored resin composition PC-21, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 22) To a mixture of 23.44 g of coloring material dispersion liquid (D-1), 23.44 g of coloring material dispersion liquid (D-3), and 5.21 g of coloring material dispersion liquid (D-5), add acrylic polymer ( 20.73 g of PGMEA 35% by weight solution of P-1), 6.92 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a multifunctional monomer, and KBM5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver A solution obtained by dissolving 0.38 g of a 10% by weight PGMEA solution of the silicone surfactant "BYK" 333 (manufactured by BYK-Chemie) as a surfactant in 19.59 g of PGMEA to obtain a total solid concentration of 25% by weight, a colored resin composition PC-22 containing 25 parts by weight of colored material relative to 100 parts by weight of the total solid content. Using the obtained colored resin composition PC-22, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 23) Colored resin composition PC-23 was obtained in the same manner as in Example 21 except that the coloring material dispersion liquid (D-6) was used instead of the coloring material dispersion liquid (D-5). Using the obtained colored resin composition PC-23, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 24) Colored resin composition PC-24 was obtained in the same manner as in Example 21 except that the coloring material dispersion liquid (D-7) was used instead of the coloring material dispersion liquid (D-5). Using the obtained colored resin composition PC-24, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 25) Colored resin composition PC-25 was obtained in the same manner as in Example 18 except that the coloring material dispersion liquid (D-8) was used instead of the coloring material dispersion liquid (D-1). Using the obtained colored resin composition PC-25, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 26) Colored resin composition PC-26 was obtained in the same manner as in Example 18 except that the coloring material dispersion liquid (D-10) was used instead of the coloring material dispersion liquid (D-3). Using the obtained colored resin composition PC-26, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 27) Colored resin composition PC-27 was obtained in the same manner as in Example 18 except that the coloring material dispersion liquid (D-9) was used instead of the coloring material dispersion liquid (D-1). Using the obtained colored resin composition PC-27, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Example 28) Colored resin composition PC-28 was obtained in the same manner as in Example 18 except that the coloring material dispersion liquid (D-11) was used instead of the coloring material dispersion liquid (D-3). Using the obtained colored resin composition PC-28, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Comparative example 1) To the mixed liquid of 41.67 g of the coloring material dispersion liquid (D-1) and 41.67 g of the coloring material dispersion liquid (D-3), 7.88 g of a 35% by weight PGMEA solution of the acrylic polymer (P-1) was added. 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 silicone-based surfactant as a surfactant A solution obtained by dissolving 0.30 g of a 10% by weight PGMEA solution of "BYK" 333 (manufactured by BYK-Chemie) in 2.94 g of PGMEA to obtain a total solids concentration of 25% by weight, relative to 100 parts by weight of the total solids. The content of the coloring material is 40 parts by weight of the coloring resin composition PC-29. Using the obtained colored resin composition PC-29, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Comparative example 2) Colored resin composition PC-30 was obtained in the same manner as in Example 1 except that the coloring material dispersion liquid (D-1) was 24.38 g and the coloring material dispersion liquid (D-3) was 2.71 g. . Using the obtained colored resin composition PC-30, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

(Comparative example 3) Colored resin composition PC-31 was obtained in the same manner as in Example 1 except that the coloring material dispersion liquid (D-1) was 2.71 g and the coloring material dispersion liquid (D-3) was 24.38 g. . Using the obtained colored resin composition PC-31, the same evaluation as in Example 1 was performed. The results are shown in Table 2.

[table 2-1] Table 2 Colored resin composition Colored resin composition (A) Resin coloring material dispersion coloring material (C) D-1 D-2 D-3 D-4 D-5 D-6 D-7 D-8 D-9 D-10 D-11 Content ^{※ 1} organic solvent Example 1 PC-1 P-1 80wt% 20wt% 13 parts by weight PGMEA Example 2 PC-2 P-1 75wt% 25wt% 13 parts by weight PGMEA Example 3 PC-3 P-1 50wt% 50wt% 13 parts by weight PGMEA Example 4 PC-4 P-1 35wt% 65wt% 13 parts by weight PGMEA Example 5 PC-5 P-1 25wt% 75wt% 13 parts by weight PGMEA Example 6 PC-6 P-1 80wt% 20wt% 25 parts by weight PGMEA Example 7 PC-7 P-1 75wt% 25wt% 25 parts by weight PGMEA Example 8 PC-8 P-1 50wt% 50wt% 25 parts by weight PGMEA Example 9 PC-9 P-1 35wt% 65wt% 25 parts by weight PGMEA Example 10 PC-10 P-1 25wt% 75wt% 25 parts by weight PGMEA Example 11 PC-11 P-1 80wt% 20wt% 6 parts by weight PGMEA Example 12 PC-12 P-1 75wt% 25wt% 6 parts by weight PGMEA Example 13 PC-13 P-1 50wt% 50wt% 6 parts by weight PGMEA Example 14 PC-14 P-1 35wt% 65wt% 6 parts by weight PGMEA Example 15 PC-15 P-1 25wt% 75wt% 6 parts by weight PGMEA Example 16 PC-16 P-1 50wt% 50wt% 30 parts by weight PGMEA Example 17 PC-17 P-1 50wt% 50wt% 35 parts by weight PGMEA Example 18 PC-18 P-1 50wt% 50wt% 39 parts by weight PGMEA Example 19 PC-19 P-1 50wt% 50wt% 13 parts by weight PGMEA Example 20 PC-20 P-1 50wt% 50wt% 13 parts by weight PGMEA Example 21 PC-21 P-1 45wt% 45wt% 10wt% 13 parts by weight PGMEA Example 22 PC-22 P-1 45wt% 45wt% 10wt% 25 parts by weight PGMEA Example 23 PC-23 P-1 45wt% 45wt% 10wt% 13 parts by weight PGMEA Example 24 PC-24 P-1 45wt% 45wt% 10wt% 13 parts by weight PGMEA Example 25 PC-25 P-1 50wt% 50wt% 39 parts by weight PGMEA Example 26 PC-26 P-1 50wt% 50wt% 39 parts by weight PGMEA Example 27 PC-27 P-1 50wt% 50wt% 39 parts by weight PGMEA Example 28 PC-28 P-1 50wt% 50wt% 39 parts by weight PGMEA Comparative example 1 PC-29 P-1 50wt% 50wt% 40 parts by weight PGMEA Comparative example 2 PC-30 P-1 90wt% 10wt% 13 parts by weight PGMEA Comparative example 3 PC-31 P-1 10wt% 90wt% 13 parts by weight PGMEA ※1: Parts by weight based on 100 parts by weight of the total solid content

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

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

It can be seen that the colored resin composition of the Example has high visible light shielding properties and near-infrared transmittance in a film thickness with an OD value of 4.0, and furthermore, the reflection chromaticity is also good. Furthermore, it can be seen that the transmitted chromaticity is also good even in a film thickness with an OD value of 1.0. On the other hand, a colored resin composition in which the content ratio of the colored material in the total solid content is large results in a large a* value of the reflection chromaticity, and the image reflected in the colored film is reddish. On the other hand, in a colored resin composition in which the ratio of the imine-based pigment to the total amount of the coloring material is large, the x and y of the transmitted chromaticity are large, and the transmitted color of the colored film is yellow. On the other hand, the coloring resin composition in which the ratio of dibenzofuranone-based pigments to the total amount of the coloring material is large has the following results, that is, the x and y of the transmitted chromaticity are small, and the transmission color band of the coloring film is small. blue. (industrial availability)

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 near-infrared camera concealment, and/or a light-shielding film for black-view mode icons.

Figure 1 is an X-ray diffraction curve of the colored film obtained in Example 3.

Claims (14)

A colored resin composition containing (A) a resin and (B) a coloring material, and containing at least a methimine-based pigment and a bisbenzofuranone-based pigment as the above-mentioned (B) coloring material. When all the coloring materials are combined When the weight is set to 100 parts by weight, the content of the imine pigment is 25 to 80 parts by weight, and the content of the dibenzofuranone pigment is 20 to 75 parts by weight, and the content of the above-mentioned (B) coloring material is relatively The total content of solid components is 1 to 39 parts by weight based on 100 parts by weight. The colored resin composition according to claim 1, wherein the crystallite size of the methimine pigment is 10 nm or more and 25 nm or less, as determined by the following measurement method, ＜Measurement method of crystallite size＞ The colored resin composition is coated on a glass substrate, dried, and heated to obtain a film. The obtained film is peeled off and placed in an aluminum standard sample holder; for this sample, X-ray winding is used X-ray device, set the X-ray source to CuKα rays, and measure the X-ray diffraction spectrum by wide-angle X-ray diffraction method; regarding the measurement conditions, the output is 40 kV/40 mA, and the slit system is Div. Slit: 0.3 °, the measurement step distance (2θ) is 0.0171°, and the measurement time is 0.5 seconds/step; the diffraction angle and half-maximum width from the main peak of the pigment are measured and calculated using Scherrer's formula. The colored resin composition of claim 1 or 2, wherein the crystallite size of the bisbenzofuranone pigment is 10 nm or more and 25 nm or less, as determined by the method for measuring the crystallite size. The colored resin composition according to any one of claims 1 to 3, wherein the crystallite size of the methimine pigment as determined by the method for measuring the crystallite size is α (nm), and When the crystallite size of the above-mentioned bisbenzofuranone-based pigment is β (nm), it is 3.0≦|α-β|≦10.0. The colored resin composition according to any one of claims 1 to 4, which contains an alkali-soluble resin as the above-mentioned (A) resin, and further contains (D) a photosensitizer and (E) a radically polymerizable compound. The colored resin composition according to any one of claims 1 to 5, wherein the transmitted color (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 6, wherein in a film formed on an alkali-free glass with a thickness of 0.7 mm so that the optical density (OD value) becomes 4, the film from the glass surface is The chromaticity values (a*, b*) measured by the reflection chromaticity measured by the SCI method are -0.5≦a*≦1.0 and -1.0≦b*≦0.5. A colored film containing (A) a resin and (B) a coloring material, and containing at least a formimine pigment and a bisbenzofuranone pigment as the above-mentioned (B) coloring material. When the weight of all the coloring materials is When it is 100 parts by weight, the content of the imine pigment is 25 to 80 parts by weight, and the content of the dibenzofuranone pigment is 20 to 75 parts by weight, and the content of the above-mentioned (B) coloring material is relative to the solid The total content of the ingredients is 1 to 39 parts by weight per 100 parts by weight. The colored film of claim 8, wherein the crystallite size of the bisbenzofuranone pigment is 10 nm or more and 25 nm or less, as determined by the following measurement method, ＜Measurement method of crystallite size＞ The colored film is placed in an aluminum standard sample holder. For this sample, an X-ray diffraction device is used, the X-ray source is set to CuKα rays, and the X-rays are measured by the wide-angle X-ray diffraction method. Diffraction spectrum; regarding the measurement conditions, the output is 40 kV/40 mA, the slit system is Div. Slit: 0.3°, the measurement step (2θ) is 0.0171°, the measurement time is 0.5 seconds/step; the main peak from the pigment is measured The diffraction angle and half-maximum width are calculated using Scherrer's formula. The colored film according to claim 8 or 9, wherein the crystallite size of the methimine pigment as determined by the above measurement method is 10 nm or more and 25 nm or less. The colored film according to any one of claims 8 to 10, wherein the crystallite size of the methimine pigment as determined by the method for measuring the crystallite size is α (nm), and the double crystallite size is α (nm). When the crystallite size of the benzofuranone-based pigment is β (nm), it is 3.0≦|α-β|≦10.0. The colored film according to any one of claims 8 to 11, wherein the following transmission chromaticity (x, y) of the above-mentioned colored film is 0.23≦x≦0.36 and 0.24≦y≦0.36, and the above-mentioned transmission chromaticity (x, y) y) is determined by making light directly incident on the film surface, and converted into the transmitted chromaticity (x, y) when the optical density (OD value) is the equivalent film thickness of 1. The colored film according to any one of claims 8 to 12, wherein the chromaticity value (a*, b*) of the following reflection chromaticity of the colored film is 0.0≦a*≦1.0 and -1.0≦b*≦ 0.0, the chromaticity values (a*, b*) of the above-mentioned reflection chromaticity are obtained by making light directly incident on the film surface, and converted into an optical density (OD value) of 4 by the SCI method when the equivalent film thickness The chromaticity value (a*, b*) of the measured reflection chromaticity. A decorative substrate provided with a substrate and the colored film according to any one of claims 8 to 13.