JP2006209102A - Black resin composition for display element and member for display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a black resin composition for a display element, which can realize a high optical density even in the case of a relatively low light shielding material content and can achieve a high optical density even in a thin film form, and to provide a member for a display element which can reduce uneven display derived from a level difference due to the film thickness of a black resin composition in a pixel part. <P>SOLUTION: The black resin composition for a display element comprises at least black titanium oxynitride and a curable binder system. The black titanium oxynitride is represented by composition formula of TiNxOy-nSiO<SB>2</SB>, wherein each of x and y represents a real number more than 0 and less than 2, and n is a real number in the range of 0≤n≤0.05; the black titanium oxynitride contains a nitrogen atom represented by N in an amount of not less than 17 wt.% and less than 23 wt.%, has a specific surface area in the range of 5 to 30 m<SP>2</SP>/g and has a crystalline diameter of 17 to 25 nm as measured with an X-ray diffractometer. The member for a display element comprises a light shielding layer formed using the black resin composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a black resin composition for a display element, and a member for a display element such as a color filter used in a liquid crystal display device or the like using the black resin composition.

The display element member includes a color filter used for a liquid crystal display device or the like. As an example, a typical example of a color filter structure used in a liquid crystal display device will be described with reference to FIG.
In general, as shown in FIG. 1A, a color liquid crystal display device (101) is provided with a gap portion 3 of about 1 to 10 μm with a color filter 1 and an electrode substrate 2 such as a TFT substrate facing each other. 3 is filled with a liquid crystal compound L, and the periphery thereof is sealed with a sealing material 4. The color filter 1 has a light shielding layer (black matrix layer) 6 formed in a predetermined pattern on the transparent substrate 5 to shield the boundary between pixels, and a plurality of colors (usually normal) to form each pixel. , Red (R), green (G), and blue (B) are arranged in a predetermined order, the pixel portion 7, the protective film 8, and the transparent electrode film 9 are arranged in this order from the side close to the transparent substrate. It has a laminated structure. An alignment film 10 is provided on the inner surface side of the color filter 1 and the electrode substrate 2 facing the color filter 1. Furthermore, a spacer is provided in the gap portion 3 in order to maintain a constant and uniform cell gap between the color filter 1 and the electrode substrate 2. As the spacer, a pearl 11 having a constant particle diameter is dispersed, or a columnar spacer 12 having a height corresponding to the cell gap as shown in FIG. 6 is formed in a region overlapping with the position where 6 is formed. A color image is obtained by controlling the light transmittance of each of the pixels colored in each color or the liquid crystal layer behind the color filter.

As described above, a color filter is generally provided with a light shielding layer that blocks light between red, green, and blue pixels. This light shielding layer improves the contrast ratio between light and dark.
As the light shielding layer, a light shielding inorganic thin film such as a chromium single layer thin film or a chromium / chromium oxide laminated thin film has been widely used. However, the light-shielding inorganic thin-film light-shielding layer using chromium has a problem that a vacuum process is required to form a thin film, resulting in an increase in manufacturing cost, and waste has a serious adverse effect on the environment.

  In order to solve such problems, a resin light shielding layer in which light shielding particles such as carbon black and titanium black are dispersed in a resin has been proposed. However, the resin light-shielding layer has a problem that the optical density (OD value) per unit film thickness is smaller than that of the inorganic thin-film light-shielding layer. For this reason, a resin light-shielding layer having a thickness of 1 μm or more is usually required to increase the contrast of light and darkness of the liquid crystal display panel and maintain high image quality.

  However, with the recent demand for color filter thinning and high performance, it is desired to make the film thin while keeping the OD value high. In addition, as shown in FIG. 2, the normal color filter has a structure in which the pattern of the pixel film 7 partially runs on the light shielding layer 6. The step 22 between the pixel surface 20 and the apex 21 of the portion that has climbed on the light shielding layer increases as the thickness of the light shielding layer increases. If this step is large, the alignment of the liquid crystal is disturbed. Therefore, when using a resin light-shielding layer as the light-shielding layer, a transparent flattening film called an overcoat is formed after the pixel film is formed. It is common to reduce. The cost of forming the flattening film has become a big problem when using the resin light-shielding layer. From this point of view, it is desired to reduce the film thickness while keeping the OD value high.

  As a means for reducing the film thickness while keeping the OD value high, for example, Patent Document 1 discloses that the optical density per unit film thickness is 4.4 / μm or more, the film thickness is 0.9 μm or less, and the surface It is disclosed that a resin black matrix having a roughness of 30 nm or more is formed by using a paste for forming a resin black matrix in which 25 to 75% by weight of constituent components are graphite fine particles having an average particle size of 100 to 400 nm. Yes. However, since graphite is a scaly crystal, it is used as a light-shielding particle and when applied on a substrate, each crystal reflects the incident light in a specular shape, increasing the overall reflectivity, and the display device There is a risk of lowering the contrast. For this reason, it has been desired to use other light-shielding particles.

On the other hand, resin light shielding layers using titanium oxynitride particles in which part of oxygen in titanium dioxide is replaced with nitrogen are mainly used as light shielding layers for high resistance. Among them, for example, Patent Document 2 is disclosed as an object for obtaining a high OD value. In Patent Document 2, the optical density (OD value) of the black coating is 3.0 or more per 1.0 μm thickness, and the adhesion strength when the contact area with glass is 5 mm ² is 5.0 MPa or more. As a means for realizing a resin black matrix characterized by having a composition of TiNxOy (where 0 <x <2.0, 0.1 <y <2.0), titanium dioxide or titanium hydroxide is used. A method of high-temperature reduction in the presence of ammonia (Japanese Patent Laid-Open Nos. 60-65069 and 61-201610), a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide, and a high-temperature reduction in the presence of ammonia ( JP, 61-201610, A) discloses the use of titanium oxynitride produced. Patent Document 3 discloses a black coating composition containing titanium oxynitride and a resin as essential components, and the diffraction angle 2θ of titanium oxynitride when CuKα rays are used as an X-ray source is 25 ° to When the maximum diffraction line intensity at 26 ° is I ₁ , the maximum diffraction line intensity at 27 ° to 28 ° is I ₂ , and the maximum diffraction line intensity at 36 ° to 38 ° is I ₃ , the following formula (1 ) X-ray intensity ratio represented by _{R R = I 3 / [I} 3 + 1.8 × (I 1 + 1.8 × I 2)] (1) is 0.24 or more, and the optical density (OD value) film A black coating composition is described which is 3.0 or more per 1 μm thickness. However, the titanium oxynitride described in Patent Document 3 has a titanium dioxide peak that has a diffraction angle 2θ of 25 to 26 ° (A type) or 27 to 28 ° (R type). It is assumed that titanium dioxide that has not been fully reduced to titanium oxynitride so that I _{1 and} I ₂ are also present in the examples.

JP 2004-93656 A Japanese Patent Laid-Open No. 2004-4651 JP 2000-143985 A

However, in Patent Document 2, although an OD value of 3.0 or more per 1.0 μm of film thickness is shown, actual thinning is not attempted, and even when using the titanium oxynitride disclosed above, It was insufficient to keep the OD value high by making the film thin enough to reduce the step. Patent Document 3 also shows an OD value of 3.0 or more per 1.0 μm film thickness, but has not actually attempted to reduce the film thickness, and titanium oxynitride that contains titanium dioxide disclosed above. Even if an object was used, it was insufficient to keep the OD value high by making the film thin enough to reduce the level difference.
In addition, if the composition for forming the resin light-shielding layer has photosensitivity, it is possible to apply the composition and pattern the resin light-shielding layer only by the steps of exposure and development. This is preferable because it can greatly contribute to the production. In order to reduce the thickness of the resin light-shielding layer while maintaining a high OD value, it is conceivable to increase the content ratio of the light-shielding material in the resin light-shielding layer. The resin component content ratio in the layer is reduced. When the resin component is used with a photosensitive property so that the resin light shielding layer can be formed by patterning, there is a problem that if the resin component ratio in the resin light shielding layer is decreased, the resin light shielding layer cannot be patterned. Further, there is a limit to increasing the content ratio of the light shielding material in the resin light shielding layer. Therefore, there has been a demand for a light shielding material that achieves a high OD value even with a relatively small content ratio.

  The present invention has been accomplished in view of the above-mentioned circumstances, and the first object thereof is to realize a high optical density even when the black pigment is contained in a relatively small amount, and to achieve a high optical density with a thinner film. It is providing the black resin composition for display elements which can implement | achieve.

  Furthermore, the second object of the present invention is a display element member produced by using a black resin composition that achieves the above object, wherein display unevenness due to a step due to the film thickness of the black resin composition in the pixel portion is reduced. Is to provide.

  In the study of a black pigment that achieves a high optical density even with a relatively small content ratio, the present inventors include titanium oxynitride produced by reacting ammonia gas or the like with titanium dioxide or the like. Visible light with a black color due to its size effect by increasing the amount of nitrogen to 17 wt% or more and less than 23 wt% and reducing the size of the crystallites constituting the titanium oxynitride particles to a range of 17 to 25 nm. In addition to absorption of light, it has been found that it has excellent concealability (light-shielding property) by utilizing reflection of visible light due to high nitridation degree, and using a predetermined titanium oxynitride dramatically improves the light-shielding property of the coating film As a result, the present invention has been completed.

That is, the black resin composition for display elements according to the present invention has a composition formula: TiNxOy · nSiO ₂ (in the composition formula, Ti represents a titanium atom, N represents a nitrogen atom, O represents an oxygen atom, Si represents a silicon atom, x Represents the ratio of nitrogen atoms to titanium atoms, y represents the ratio of oxygen atoms to titanium atoms, and x and y can each be a real number greater than 0 and less than 2. n represents the molar ratio of SiO _{2 to} TiNxOy, n can take a real number in the range of 0 ≦ n ≦ 0.05.), and includes a nitrogen atom represented by N in a range of 17 wt% or more and less than 23 wt%, and has a specific surface area of At least a black titanium oxynitride characterized by having a crystallite diameter in the range of 5 to 30 m ² / g and a crystallite diameter measured using an X-ray diffractometer in the range of 17 to 25 nm, and a curable binder system To do.

  The black resin composition for a display element according to the present invention has a specific composition, a high content of nitrogen atoms, and a combination of a titanium oxynitride having a predetermined crystallite diameter and a curable binder system. In order to realize a high optical density even if the content of titanium oxynitride is relatively small, a high optical density can be achieved even if a thin film is formed. Furthermore, since the black resin composition for display elements according to the present invention can have a relatively high binder content, patterning can be easily realized when the binder system is photosensitive, and the process can be simplified. Can greatly contribute to the development, and the application range can be expanded. That is, the black resin composition for a display element according to the present invention can have a patterning property while realizing a high optical density even when a thin film is formed.

  In the black resin composition according to the present invention, the titanium oxynitride has a reflectance at a wavelength of 650 nm measured using an ultraviolet-visible spectrophotometer of at least 11% and a reflection in a wavelength range of 400 to 800 nm. The minimum value of the ratio is preferably 11.5% or less from the viewpoint that a higher optical density can be realized.

In the black resin composition according to the present invention, since the titanium oxynitride and TiNxOy · nSiO ₂ contain nitrogen atoms represented by N in a range of 19 to 22% by weight, higher optical density can be realized. preferable.

  In the black resin composition according to the present invention, a higher optical density can be realized when the ratio y / x of y to x represented by TiNxOy of titanium oxynitride is in the range of 0.10 to 0.60. From this point, it is preferable.

  In the black resin composition according to the present invention, the particle surface of the titanium oxynitride is coated with an inorganic compound and / or an organic compound in a range of 0.01 to 30% by weight with respect to titanium oxynitride. It is preferable from the viewpoint of the dispersibility and dispersion stability of the particles.

  Further, in the black resin composition according to the present invention, the curable binder system is preferably photosensitive because it allows easy patterning, greatly contributes to simplification of the process, and widens the application range. .

  Furthermore, in the black resin composition according to the present invention, when the compound represented by the following formula (1) is included in the curable binder system, the sensitivity of the photosensitive black resin composition is improved, and a higher optical density is obtained. When it is going to be realized, it is preferable because it can be sufficiently cured even if it contains a relatively large amount of titanium oxynitride.

（式中、Ｒ¹乃至Ｒ¹⁴は、それぞれ独立して水素、ヒドロキシル基、アミノ基、カルボキシル基、ハロゲン、ケトン基、芳香族基、又は脂肪族基のいずれかである。但し、前記芳香族基及び脂肪族基は、分岐構造及び脂環式構造から選ばれる構造を含んでいても良く、基の途中にエーテル結合、エステル結合、アミノ結合、アミド結合、チオエーテル結合、不飽和結合から選ばれる１種以上を含んでいても良く、基の末端にヒドロキシル基、アミノ基、カルボキシル基、ハロゲン、カルボニル基、芳香族基から選ばれる１種以上を含んでいても良い。）

(In the formula, R ^{1 to} R ¹⁴ are each independently hydrogen, hydroxyl group, amino group, carboxyl group, halogen, ketone group, aromatic group, or aliphatic group. The group and the aliphatic group may include a structure selected from a branched structure and an alicyclic structure, and are selected from an ether bond, an ester bond, an amino bond, an amide bond, a thioether bond, and an unsaturated bond in the middle of the group. One or more kinds may be contained, and one or more kinds selected from a hydroxyl group, an amino group, a carboxyl group, a halogen, a carbonyl group, and an aromatic group may be contained at the terminal of the group.

Furthermore, it is preferable that carbon black is contained in an amount of 3 to 20% by weight based on the entire pigment containing titanium oxynitride from the viewpoint of reducing colored reflected light.
Furthermore, in the black resin composition according to the present invention, when the binder system is photosensitive, the weight ratio (P / V) between the pigment (P) containing titanium oxynitride and the solid content (V) other than the pigment is 0. It is preferable from the point of light-shielding property and patterning property that it is 0.5-3.0.

  In addition, the black resin composition according to the present invention is suitable for a light shielding layer, and is suitable for use in a color filter among display element members.

  Next, the display element member according to the present invention includes a light shielding layer formed using the black resin composition for display element according to the present invention.

  Since the display element member according to the present invention includes a light-shielding layer formed using the black resin composition according to the present invention, it can be a thin-film light-shielding layer having a sufficient optical density. Therefore, it is possible to cope with a thin film and high performance optical element, and further, it is possible to reduce a step of the pixel portion, thereby reducing display unevenness.

  In the black resin composition for display elements according to the present invention, since titanium oxynitride has excellent light-shielding properties, a high optical density can be realized even if its content is relatively small. Can be realized with a thin film thickness, and a higher optical density can be realized with a conventional film thickness.

  Furthermore, since the black resin composition for display elements according to the present invention can relatively increase the content ratio of the binder system, patterning can be easily realized and the process can be simplified when the binder system is photosensitive. Can greatly contribute to the development, and the application range can be expanded. That is, the black resin composition for a display element according to the present invention can have a patterning property while realizing a high optical density even when a thin film is formed.

  Moreover, the display element member according to the present invention includes a light-shielding layer formed using the black resin composition for display elements according to the present invention, thereby forming a thin-film light-shielding layer having a sufficient optical density. Therefore, it is possible to cope with a thin film and high performance optical element, and further, the step of the pixel portion can be lowered, so that display unevenness can be reduced.

  The present invention is described in detail below. In the present invention, the light includes electromagnetic waves having wavelengths in the visible and non-visible regions, and further includes radiation, and the radiation includes, for example, microwaves and electron beams. Specifically, it means an electromagnetic wave having a wavelength of 5 μm or less and an electron beam. In the present invention, (meth) acryl means either acryl or methacryl, (meth) acrylate means either acrylate or methacrylate, and (meth) acryloyl is , Meaning either acryloyl or methacryloyl.

1. Black resin composition for display element The black resin composition for display element according to the present invention has a composition formula: TiNxOy · nSiO ₂ (in the composition formula, Ti is a titanium atom, N is a nitrogen atom, O is an oxygen atom, and Si is silicon) X represents the ratio of nitrogen atoms to titanium atoms, y represents the ratio of oxygen atoms to titanium atoms, and x and y can each be a real number greater than 0 and less than 2. n is the ratio of SiO _{2 to} TiNxOy. N represents a real number in the range of 0 ≦ n ≦ 0.05, and includes a nitrogen atom represented by N in the range of 17 wt% or more and less than 23 wt%, and the ratio A black titanium oxynitride characterized in that the surface area is in the range of 5 to 30 m ² / g and the crystallite diameter measured with an X-ray diffractometer is in the range of 17 to 25 nm, and a curable binder system Contains at least.

The black resin composition for display elements according to the present invention has a specific composition, a high nitrogen content, and a combination of a titanium oxynitride having a predetermined crystallite diameter and a curable binder system, Even when the content of titanium oxynitride is relatively small, a high optical density can be realized, so that a high optical density can be realized even if a thin film is formed. Furthermore, since the black resin composition for display elements according to the present invention can relatively increase the content ratio of the binder system, patternability can be easily realized when the binder system is photosensitive, It can greatly contribute to simplification and can expand the application range. That is, the black resin composition for display elements according to the present invention can have patterning properties while achieving high optical density even when a thin film is formed.
First, each component mix | blended with the black resin composition for display elements of this invention is demonstrated.

<Titanium oxynitride>
(1) Composition of titanium oxynitride The titanium oxynitride of the present invention is represented by TiNxOy, and may contain silicon oxide represented by SiO _{2 as} necessary. Silicon oxide forms a mixture with titanium oxynitride. Or may be adhered to the surface of the titanium oxynitride particles, or may be formed into a composite with the titanium oxynitride or may be dissolved in the titanium oxynitride particles. From this, the titanium oxynitride of the present invention is represented by the composition formula: TiNxOy · nSiO ₂ , where Ti represents a titanium atom, N represents a nitrogen atom, O represents an oxygen atom, Si represents a silicon atom, and x represents The ratio of nitrogen atom to titanium atom, y represents the ratio of oxygen atom to titanium atom, and n represents the molar ratio of SiO _{2 to} TiNxOy. x and y can each be a real number greater than 0 and less than 2, but in order to obtain particles having good oxidation stability and a desired high degree of nitridation, the ratio y / x to x is 0.10 to 0. .60, preferably 0.15 to 0.50, more preferably 0.15 to 0.40, and most preferably 0.15 to 0.30.

Titanium oxynitride may or may not contain silicon oxide, but silicon oxide prevents sintering during the production of titanium oxynitride, promotes nitriding, oxidation stability of titanium oxynitride, oxynitriding Expected to have a dispersion effect when titanium is dispersed in a resin or a solvent, it may be anhydrous silicon oxide, silicon oxide adsorbed with moisture, or in the form of hydrous silicon oxide. When used for production at a high temperature, it tends to be anhydrous silicon oxide. Silicon oxide is thought to exist in the state of SiO ₂ , but when titanium oxynitride is produced, if it is fired at high temperature with ammonia gas, amine gas, etc., part of silicon oxide is nitrided to produce oxynitride or nitride In some cases, silicon oxynitride or silicon nitride may be present in the present invention. The molar ratio n of the silicon oxide contained can take a real number in the range of 0 ≦ n ≦ 0.05, preferably in the range of 0.001 ≦ n ≦ 0.04, and in the range of 0.003 ≦ n ≦ 0.03. Is more preferable.

Titanium and silicon atoms are analyzed by ICP emission spectroscopy, oxygen atoms are analyzed using an inert gas carrier melting infrared absorption method, and nitrogen atoms are analyzed by a carbon / hydrogen / nitrogen analyzer. x and n are calculated. If a silicon atom is present, it is assumed that the silicon atom is bonded to an oxygen atom to form silicon oxide SiO ₂ , and the oxygen atom component that is bonded to the silicon atom and becomes SiO ₂ is subtracted from the analysis value of the oxygen atom. The value obtained is taken as the value of oxygen atoms in TiNxOy, and y is calculated from that value.

(2) Nitrogen content and oxygen content of titanium oxynitride It is important for the TiNxOy · nSiO ₂ that the nitrogen content represented by N is 17 wt% or more and less than 23 wt%, 19-22 wt% Is more preferable, and the range of more than 20% by weight and not more than 22% by weight is more preferable. When the nitrogen content is 17% by weight or more, particularly when it exceeds 20% by weight, it has a reddish black color. However, when it is blended in a coating film, it exhibits a metallic luster and increases the reflectance of visible light. , The concealing property (light shielding property) is increased. The titanium nitride TiN composition contains about 23% by weight of nitrogen, but the nitrogen content of the titanium oxynitride of the present invention is less.

  On the other hand, the oxygen content represented by O in TiNxOy is preferably in the range of 0.5 to 15% by weight because oxidation is difficult to proceed with time and is stable, preferably 1 to 13% by weight. The range is more preferable, the range of 2 to 11% by weight is further preferable, the range of 3 to 10% by weight is further preferable, and the range of 4 to 9% by weight is most preferable.

(3) X-ray diffraction of titanium oxynitride In the X-ray diffraction of titanium oxynitride (using Cuα rays), the main (first) peak is 2θ between 40 and 45 °, and the second is between 35 and 40 °. A peak can be observed, and the angle of the first peak gradually shifts when the nitrogen content is changed. For example, when x of TiNxOy is from 0.85 to 1, the peak position shifts to the lower angle side as the value of x increases. When x is about 0.95, 2θ is about 42.9 ° and x is about 0.2. If it is about 93, 2θ is about 43.0 °, and if x is about 0.89, 2θ is about 43.2 °. The main (first) peak of the titanium oxynitride of the present invention is different from the peak position (42.6 °) of titanium nitride, and on the higher angle side, for example, in the range of 42.7 ° to 43.5 °. Thus, the titanium oxynitride of the present invention is different from titanium nitride or a partially oxidized surface thereof. Titanium oxynitride is a titanium oxide such as titanium dioxide, hydrous titanium oxide, titanium hydroxide, low-order titanium oxide such as TiO, Ti ₂ O ₃ , Ti ₃ O _5, etc., heated in the presence of ammonia gas, amine gas, etc. Since it is obtained by firing, when the titanium oxide used as the starting material remains, an X-ray diffraction peak derived from titanium dioxide or the like can be confirmed. It is preferable to reduce to an extent that cannot be confirmed. In addition, the peak position of the X-ray diffraction of titanium dioxide appears between 25-26 ° as 2θ for anatase-type titanium dioxide and 27-28 ° as 2θ for rutile-type titanium dioxide. On the other hand, the X-ray diffraction peak of silicon oxide cannot be confirmed even when a considerable amount thereof exists.

  The size of the crystallites constituting the titanium oxynitride particles can be determined from the half width of the X-ray diffraction main (first) peak of titanium oxynitride using the Scherrer formula of Formula 1. Commercially available titanium black has a crystallite diameter of 26 nm, but it is important for the titanium oxynitride of the present invention to have a crystallite diameter in the range of 17 to 25 nm. Even if it is high, it is preferable because it has relatively high blackness, more preferably in the range of 19 to 24 nm, still more preferably in the range of 19.5 to 23 nm, and most preferably in the range of 20 to 22 nm.

Formula 1: D = 0.9λ / (β _1/2 × cos θ)
(In Formula 1, D is the calculated crystallite diameter (Å), λ is the X-ray wavelength, and uses the Cu α-ray wavelength of 1.54Å. Β _1/2 is the half width of the main (first) peak (In radians, θ represents the reflection angle.)

(4) Titanium oxynitride blackness Titanium oxynitride has a blackish color and has a bluish black, purplish black, reddish black, and brownishness in addition to pure black Other colors besides black, such as black, may be exhibited. As for the brightness and hue of titanium oxynitride, 1.5 g of a sample was put in a glass round cell (Nippon Denshoku, part No. 1483), and from the bottom of the cell, a color difference meter (Nippon Denshoku Color Meter ZE2000) was used. The color is measured and determined by the Lab color system. The blackness is represented by the lightness index L value of the Lab color system, and the smaller the L value, the stronger the blackness. In the titanium oxynitride of the present invention, for example, the L value has a blackness of about 2 to 20 Preferably about 8-13.

  In addition, the Lab color system a value and b value obtained in the same manner as the L value are indices representing hue saturation, and the redness increases as the a value increases toward the positive side and the greenness increases as the value increases toward the negative side. It shows that it is strong, yellow value is so strong that b value becomes large on the positive side, and blue color is so strong that it becomes large on the negative side. The titanium oxynitride of the present invention can have a hue having an a value of about 2-5 and a b value of about -1-5.

(5) Visible light reflectivity of titanium oxynitride Titanium oxynitride has a blackish color and thus has a large absorption of visible light. However, in order to further improve the concealability, in addition to the absorption of visible light, visible light It is conceivable to utilize the reflection of light. That is, as the minimum value of the reflectance in the wavelength range of 400 to 800 nm is smaller and the reflectance in the long wavelength region of visible light is higher, higher shielding properties (light shielding properties) can be obtained. For reflection of visible light, 0.3 g of titanium oxynitride powder was packed in a cylindrical cell (diameter 16 mm, JASCO PSH-001 type) using a UV-visible spectrophotometer (JASCO V-570). When the reflection spectrum is measured (barium sulfate powder is used as a comparative sample), there is a wavelength of light having a minimum reflectance in the wavelength range of 400 to 800 nm, and light having a longer wavelength is generally reflected. It is said. For this reason, the reflection of visible light can be increased by shifting the wavelength of light exhibiting the minimum value of the reflectance to the lower wavelength side due to the composition change of titanium oxynitride or the like.

  As a result of research from this point of view, the titanium oxynitride of the present invention has a high degree of nitridation and a small crystallite diameter, so the wavelength that shows the minimum value of reflectivity shifts to the lower wavelength side due to its size effect. If the wavelength showing the minimum value of the reflectance is about 550 nm or less, a desired reflection effect is obtained, and about 490 nm or less is more preferable. The minimum value of the reflectance varies depending on the crystallite diameter, specific surface area, nitridation degree, etc. of titanium oxynitride, but the titanium oxynitride of the present invention has a specific crystallite diameter, specific surface area, and nitrogen content. Therefore, the minimum value of the reflectance can be reduced, and the absorptance at the wavelength can be increased. The minimum value of reflectance measured in the wavelength range of 400 to 800 nm is preferably 11.5% or less.

  Further, when the reflectance of visible light is represented by the reflectance at a wavelength of 650 nm (red light), it is preferably at least about 11%, more preferably at least about 13%, and at least about 14%. More preferably, it is at least about 15%. Therefore, in the present invention, the reflectance at a wavelength of 650 nm is at least 11%, and the wavelength indicating the minimum value of the reflectance is 550 nm or less, and the minimum value of the reflectance is 11.5% or less. Some are preferable from the viewpoint that a higher optical density can be realized.

(6) Particle diameter of titanium oxynitride The particles of TiNxOy · nSiO ₂ are preferably observed when observed with an electron microscope and the particle diameter is in the range of 0.02 to 0.5 μm because of excellent concealability. The range of 02 to 0.25 μm is more preferable, the range of 0.03 to 0.2 μm is still more preferable, and the range of 0.03 to 0.1 μm is most preferable. Here, the particle diameter means an average particle diameter. When silicon oxide is included, its presence cannot be confirmed with an electron microscope, but it is assumed that silicon oxide is attached to the surface of the titanium oxynitride particles.

(7) Specific surface area of titanium oxynitride When the specific surface area of titanium oxynitride is in the range of 5 to 30 m ² / g as measured by the BET method, it is easy to disperse with a resin binder or dispersant, and has good concealment properties. Therefore, it is more preferable that it is the range of 10-25 m < ² > / g.

(8) Method for producing titanium oxynitride The titanium oxynitride of the present invention is heated and fired by raising the temperature of the apparatus loaded with titanium oxide in the presence of a nitrogen-containing reducing agent to a temperature in the range of about 750 to 1200 ° C. Can be manufactured. The heating and firing temperature is preferably in the range of about 850 to 1100 ° C, more preferably about 950 to 1050 ° C, and most preferably about 970 to 1000 ° C. In the present invention, titanium oxynitride having a high degree of nitriding and a small crystallite diameter can be obtained by optimizing the heating and firing temperature. When the heating and baking temperature is lower than the above range, nitriding is difficult to proceed and it is difficult to obtain desired titanium oxynitride, and when it is higher than the above range, sintering is advanced and it is difficult to obtain fine particles. The heating and firing time varies depending on the amount of the titanium oxide and the nitrogen-containing reducing agent, and is appropriately set. However, about 1 to 20 hours is appropriate for operation, and about 3 to 10 hours is preferable. Moreover, after performing heat baking, it may cool, and heat baking may be repeated repeatedly after that. As the heating and baking apparatus, a known apparatus such as a fluidized bed apparatus, a rotary kiln, or a tunnel kiln can be used, and a rotary kiln is particularly preferable. As the nitrogen-containing reducing agent, for example, ammonia, alkylamines such as methylamine and dimethylamine, hydrazine and hydrazine-based compounds such as hydrazine sulfate and hydrazine hydrochloride, and the like can be used. You may mix and use. Among these, ammonia and alkylamine are preferable because they can be made into a gaseous state and brought into contact with the titanium oxide and easily reacted uniformly. Furthermore, it is preferable to add a small amount of nitrogen, hydrogen, or hydrocarbon to these nitrogen-containing reducing agents because nitriding can be promoted. In particular, a hydrocarbon is preferable because it reacts with oxygen in the titanium oxide to become carbon dioxide, and generation of water that suppresses the nitriding reaction can be suppressed.

The titanium oxide referred to in the present invention is not only a normal rutile type (R type) or anatase type (A type) titanium dioxide, but also hydrated titanium oxide, hydrous titanium oxide, titanium hydroxide, TiO, Ti ₂ O. ₃ and a compound including low-order titanium oxide such as Ti ₃ O ₅ . Titanium dioxide is obtained, for example, by heating and baking hydrous titanium oxide (or titanium hydroxide) at a temperature of about 800 to 1000 ° C. in an atmosphere of air or oxygen-containing gas or in an inert gas atmosphere such as nitrogen or argon. It is done. In addition, hydrous titanium oxide is obtained by, for example, grinding titanium-containing ores such as illuminite ore and titanium slag as necessary, and reacting the titanium component and sulfuric acid while dissolving with sulfuric acid to produce titanyl sulfate (TiOSO ₄ ). It is obtained by standing, classifying and filtering, and then hydrolyzing titanyl sulfate with heating. In the nitriding reaction in which titanium oxide is heated and fired in the presence of a nitrogen-containing reducing agent, it is difficult to proceed with nitriding in the presence of water. Anatase type titanium dioxide is more preferable than rutile type because it is more easily nitrided.

  In the present invention, when silicon oxide is coated on the surface of titanium oxide particles and then heated and fired, the particles are difficult to sinter even at a high temperature within the above range, and further, rutile titanium dioxide is not easily generated in the reaction process. Therefore, nitriding is easy to proceed, and fine titanium oxynitride is more easily obtained, which is preferable. Silicon oxide may be coated as porous silicon oxide or dense silicon oxide, but coating as dense silicon oxide is preferable because an effect of suppressing sintering can be easily obtained. The coating amount of silicon oxide may be an amount that represents a range of 0 <n ≦ 0.05 in terms of a molar ratio n to TiNxOy obtained by heating and firing, and a range of 0.001 ≦ n ≦ 0.04. The range of 0.003 ≦ n ≦ 0.03 is more preferable. If the coating amount of silicon oxide is less than the above range, it is difficult to obtain a desired sintering suppressing effect, and if it is too large, nitriding is difficult to proceed, which is not preferable.

As a method for coating the dense silicon oxide, a known method as described in JP-A-53-33228, JP-A-7-8971, or the like can be used. The method described in JP-A-53-33228 preferably adjusts the pH of the slurry to a range of 9 to 10.5 while maintaining the titanium oxide slurry at a temperature in the range of 80 to 100 ° C. After the rapid addition of sodium silicate, it is neutralized at a pH in the range of 9 to 10.5 and then maintained at a temperature in the range of 80 to 100 ° C. for 50 to 60 minutes. In the method described in JP-A-7-8971, after adjusting the pH of the slurry of titanium oxide to the range of 9.5 to 11, it is 60 ° C or higher, preferably 70 ° C or higher, more preferably 90 ° C or higher. Under temperature, the silicate is gradually added over 30 to 120 minutes, then neutralized, and then maintained for 60 to 120 minutes while maintaining the slurry temperature. As the silicate, sodium silicate, potassium silicate and the like can be used. As the neutralizing agent, an inorganic compound such as sulfuric acid and hydrochloric acid, and an acidic compound such as organic acid such as acetic acid and formic acid can be used. it can. After coating with silicon oxide, it is preferably dehydrated and washed, and then subjected to a heating and firing step.
The porous silicon oxide coating method was performed by rapidly adding sodium silicate while maintaining the titanium oxide slurry at a temperature of 70 ° C. or less, and then neutralizing, and then reducing the temperature at 70 ° C. or less to 30 minutes or less. Is to hold during

  After producing the titanium oxynitride, if necessary, dry pulverization may be performed by a known method, or after slurrying, wet pulverization, dehydration, drying, and dry pulverization may be performed. For wet grinding, vertical sand mill, horizontal sand mill, etc., for drying, band type heater, batch type heater, etc., for dry grinding, hammer mill, pin mill etc. impact crusher, crusher etc. grinding crusher, jet An airflow crusher such as a mill or a snail mill, or a device such as a spray dryer can be used.

  The particle surface of the titanium oxynitride of the present invention is at least selected from an inorganic compound and an organic compound for the purpose of improving the affinity with a resin binder, improving the temporal stability during storage of the paint, and improving productivity. One may be coated.

  Examples of the inorganic compound include an aluminum compound, a silicon compound, a zirconium compound, a tin compound, a titanium compound, an antimony compound, and the like. They can also be used in combination, for example, by mixing and coating the above inorganic compounds. More preferably, these inorganic compounds are at least one selected from oxides, hydroxides, hydrated oxides, and phosphates.

  Examples of organic compounds include polyhydric alcohols, alkanolamines or derivatives thereof, organosilicon compounds, higher fatty acids or metal salts thereof, and organometallic compounds. Specifically, for example, (1) polyhydric alcohol includes trimethylolethane, trimethylolpropane, tripropanolethane, pentaerythritol and the like. (2) Examples of the alkanolamine include triethanolamine and tripropanolamine. (3) Examples of organosilicon compounds include: (a) polysiloxanes (dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, dimethylpolysiloxanediol, alkyl-modified silicone oil, alkylaralkyl-modified silicone oil, amino-modified silicone) Oil, both-end amino-modified silicone oil, epoxy-modified silicone oil, both-end epoxy-modified silicone oil, fluorine-modified silicone oil, etc.), (b) organosilanes (n-butyltriethoxysilane, isobutyltrimethoxysilane, n-hexyl) Trimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, n-octadecyltrimeth Non-reactive silanes such as silane, alkylsilanes such as n-octadecylmethyldimethoxysilane, phenylsilanes such as phenyltriethoxysilane, fluorosilanes such as trifluoropropyltrimethoxysilane, aminopropyltriethoxysilane, N -(Β-aminoethyl) -γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, γ-glycidoxypropyltrimethoxy Silane, and silane coupling agents such as methacryloxypropyltrimethoxysilane β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane). (4) Examples of higher fatty acids include stearic acid and lauric acid, and examples of metal salts thereof include magnesium salts and zinc salts. (5) Examples of organometallic compounds include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis ( Dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, titanium coupling agent such as isopropyltri (N-amidoethyl / aminoethyl) titanate, aluminum coupling agent such as acetoalkoxyaluminum diisopropylate, zirconium Zirconium compounds such as tributoxyacetylacetonate and zirconium tributoxy systemate are listed. These can be coated alone or in combination of two or more.

  The coating amount can be appropriately set, but is preferably in the range of about 0.01 to 30% by weight, more preferably in the range of about 0.05 to 10% by weight, and 0.1 to 5% by weight with respect to titanium oxynitride. A range of about is more preferred. When coating the surface of titanium oxynitride with an inorganic compound or an organic compound, using a known method such as a wet method or a dry method, for example, when dry pulverizing titanium oxynitride, when slurrying or when wet pulverizing It can be carried out. When surface treatment is performed by a wet method, it is preferable to wet pulverize titanium oxynitride before or during the treatment. Further, the surface treatment by the wet method can be carried out in either an aqueous system or a solvent system, but the aqueous system is preferable in terms of environment, cost, and equipment. However, when processing in aqueous system, especially when wet pulverization is performed, titanium oxynitride is slightly oxidized under the influence of water itself or dissolved oxygen in water, so hydrazine, sodium borohydride, formaldehyde, tartaric acid, glucose It is preferable to perform wet pulverization in the presence of a reducing agent such as sodium hypophosphite or NN-diethylglycine sodium.

  Titanium oxynitride is preferably blended in an amount of 33 to 75 parts by weight, more preferably 38 to 72 parts by weight, based on 100 parts by weight of the solid content of the black resin composition for display elements. Here, the solid content for specifying the blending ratio includes all components except the solvent, and liquid polymerizable monomers and the like are also included in the solid content.

<Curable binder system>
In the present invention, from the viewpoint of imparting sufficient strength, durability, and adhesion to the coating film, the coating film is cured by a polymerization reaction after forming a pattern on the substrate by coating or an inkjet method or transfer. A curable binder system is used. Examples of such a curable binder system include a photosensitive binder system that can be polymerized and cured by visible light, ultraviolet light, electron beam, and the like, and a heat that can be polymerized and cured by heating. Examples include curable binder systems such as curable binder systems. As the curable binder system used in the present invention, a photosensitive binder system, a thermosetting binder system, and a system including both a photosensitive binder system and a thermosetting binder system can be used.

(1) Photosensitive binder system The photosensitive binder system contains a photocurable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams, and the exposed area is cured to dissolve and remove the unexposed area. A negative photosensitive binder system that enables the creation of a coating film pattern only for the exposed area, and the exposed area undergoes a chemical change so that it becomes soluble in, for example, an alkaline aqueous solution. The solubility of the exposed area and the unexposed area A positive type photosensitive binder system is included that makes it possible to create a coating film pattern only in the unexposed area by dissolving and removing the exposed area using the difference.

(I) Negative photosensitive binder system The negative photosensitive binder system containing a photocurable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams is composed of (A) an alkali-soluble resin and (B) a multifunctional resin. It is composed of a monomer, (C) a photopolymerization initiator, a sensitizer and the like.

(A) Alkali-soluble resin The alkali-soluble resin in the present invention has a carboxyl group in the side chain, acts as a binder for the titanium oxynitride, and is preferably used for forming a pattern, particularly preferably An appropriate resin can be used as long as it is soluble in an alkaline developer. A preferable alkali-soluble resin in the present invention is a resin having a carboxyl group, and specific examples thereof include an acrylic copolymer having a carboxyl group and an epoxy (meth) acrylate resin having a carboxyl group. Among these, particularly preferred are those having a carboxyl group in the side chain and further having an ethylenically unsaturated group in the side chain. These acrylic copolymers and epoxy acrylate resins may be used as a mixture of two or more.

(Acrylic copolymer having a carboxyl group)
The acrylic copolymer having a carboxyl group is obtained by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer and an ethylenically unsaturated monomer.
Examples of the carboxyl group-containing ethylenically unsaturated monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, and itacone. Unsaturated dicarboxylic acids (anhydrides) such as acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; trivalent or higher unsaturated polycarboxylic acids (anhydrides); succinic acid mono (2-acrylic acid) Monopolymers of non-polymerizable dicarboxylic acids such as leuoxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) 2-acryloyloxyethyl) ester or mono (2-acryloyloxyethyl) ester; ω-carboxypolycaprola Examples include kuton monoacrylate and ω-carboxypolycaprolactone monomethacrylate. These carboxyl group-containing ethylenically unsaturated monomers can be used alone or in admixture of two or more.

  Other ethylenically unsaturated monomers include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene. Aromatic vinyl compounds such as p-methoxystyrene, indene, p-vinylbenzyl methyl ether, p-vinylbenzyl glycidyl ether; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl Tacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2- Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl Methacrylate, 2-methoxyethyl acrylate, 2-meth Unsaturated carboxylic acid esters such as xyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, glycerol monoacrylate, glycerol monomethacrylate 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethyl Aminopropyl methacrylate Unsaturated carboxylic acid aminoalkyl esters such as 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, and 3-dimethylaminopropyl methacrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and methacryl glycidyl ether; acrylonitrile, methacrylonitrile, Vinyl cyanide compounds such as α-chloroacrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide, N- Unsaturated amides such as 2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide; N-cyclohexylmaleimide, N-phenylmaleimide, N-o-hydroxy Phenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide N-substituted maleimides such as Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; polystyrene, polymethylacrylic Over DOO, polymethyl methacrylate, polymethyl -n- butyl acrylate, poly -n- butyl methacrylate, can be mentioned macromonomers or the like having a polymer molecular chain end Monoakuriroiru group or mono methacryloyl groups polysiloxane. These other ethylenically unsaturated monomers can be used alone or in admixture of two or more.

Specific examples of the acrylic copolymer having a carboxyl group include (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / styrene / methyl (meth) acrylate copolymer, (meth) acrylic. Acid / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer Polymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / glycerin Mono (meth) acrylate Benzyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / N-phenylmaleimide copolymer Coalescence,

  (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / poly Methyl methacrylate macromonomer copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / styrene / phenyl (meth) acrylate / N-phenylmaleimide copolymer Coalescence, (meth) acrylic acid / glycerin mono (meth) acrylate / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / styrene / phenyl (meth) acrylate copolymer, (Meta Acrylic acid / glycerin mono (meth) acrylate / styrene / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / methyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meta ) Acrylic acid / glycerin mono (meth) acrylate / methyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / methyl (meth) acrylate / N-phenylmaleimide Polymer, (meth) acrylic acid / glycerin mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / 2-hydroxy ethyl( T) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerin Mono (meth) acrylate / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / benzyl (Meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / benzyl ( (Meth) acrylate / polis Tylene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) (Acryloyloxyethyl) / glycerin mono (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer, ( (Meth) acrylic acid / glycerin mono (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macro Nomer copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerin mono ( (Meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / N-phenylmaleimide / polymethylmethacrylate macromonomer copolymer,

  (Meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer Copolymer, (meth) acrylic acid / styrene / phenyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / styrene / phenyl (meth) acrylate / N-phenylmaleimide / poly Methyl methacrylate macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / styrene / methyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin (Meth) acrylate / styrene / methyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / styrene / methyl (meth) acrylate / N-phenylmaleimide copolymer Copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / styrene / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer, (Meta Acrylic acid / glycerin mono (meth) acrylate / styrene / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (Meth) acrylate / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Glycerin mono (meth) acrylate / styrene / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / styrene / benzyl (meth) acrylate / polymethylmethacrylate mac Ronomer copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / styrene / phenyl (meth) acrylate copolymer,

  (Meth) acrylic acid / glycerin mono (meth) acrylate / styrene / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / styrene / phenyl (meth) acrylate / Polystyrene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / styrene / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / succinic acid mono [2- ( (Meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / styrene / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / styrene / N-phenylmaleimide / polystyrene macromono -Copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / styrene / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / methyl (meta ) Acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (Meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Glicelli Mono (meth) acrylate / methyl (meth) acrylate / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (Meth) acrylate / methyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / methyl (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide copolymer Polymer, (meth) acrylic acid / glycerin mono (meth) acrylate / methyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / methyl ( Meta) Acu Relate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / methyl (meth) acrylate / Phenyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / methyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerin Mono (meth) acrylate / methyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / methyl (meth) acrylate / phenyl (meth) acrylate DOO / polymethyl methacrylate macromonomer copolymers,

  (Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / methyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerin mono (Meth) acrylate / methyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / methyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate Macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / speech Acid mono 2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / 2 -Hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / Polystyrene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) a Rylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / glycerin Mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / Phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer Copolymer,

  (Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Glycerin mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / benzyl (meth) acrylate / phenyl (Meta) a Relate copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / benzyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / Benzyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / benzyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer Copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid Luric acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / succinic acid mono [2- (Meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide / polymethylmethacrylate macromonomer copolymer, (meth) acrylic Acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono [2- (Meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / Glycerin mono (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

(Meth) acrylic acid / glycerin mono (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / glycerin mono (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide / polymethylmethacrylate macromonomer copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer Copolymer or (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / glycerin mono (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, (meth) Acrylic acid / succinic Sanmono [2- (meth) acryloyloxyethyl] / styrene / benzyl (meth) acrylate / N- phenylmaleimide copolymer,
(Meth) acrylic acid / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / styrene / 2-hydroxyethyl (meth) Acrylate / benzyl (meth) acrylate / N-phenylmaleimide / polymethylmethacrylate macromonomer copolymer, (meth) acrylic acid / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide / Polystyrene macromonomer copolymer or (meth) acrylic acid / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer It can be mentioned copolymers.

In addition, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4- (2,3-epoxypropyl) butyl (meth) acrylate, for some carboxyl groups of the acrylic copolymer, It reacts with the epoxy group of a compound having an epoxy group and an ethylenically unsaturated group in one molecule such as allyl glycidyl ether, or a part or all of the hydroxyl groups of the acrylic copolymer, such as 2-methacryloyloxyethyl isocyanate. An acrylic copolymer having an ethylenically unsaturated group in the side chain obtained by reacting an isocyanate group of a compound having an isocyanate group and an ethylenically unsaturated group in one molecule can also be used.
Such an ethylenically unsaturated bond-containing compound itself has polymerization reactivity and can be used as a photocurable resin.

  The copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the carboxyl group-containing ethylenically unsaturated monomer is less than 5% by weight, the solubility of the resulting coating film in an alkaline developer is lowered, and pattern formation becomes difficult. On the other hand, when the copolymerization ratio exceeds 50% by weight, the pattern formed tends to fall off from the substrate and the film surface of the pattern tends to become rough during development with an alkali developer.

  The preferred molecular weight of the carboxyl group-containing copolymer is preferably in the range of 1,000 to 500,000, more preferably 3,000 to 200,000. If it is less than 1,000, the binder function after curing is remarkably lowered, and if it exceeds 500,000, pattern formation may be difficult during development with an alkaline developer.

  Conventionally, for example, prepolymers blended in UV curable resin compositions used in various fields such as inks, paints, and adhesives can also be used in the present invention. Conventionally known prepolymers include radical polymerization type prepolymers, cationic polymerization type prepolymers, thiol / ene addition type prepolymers, and any of them may be used.

  Among these, radically polymerizable prepolymers can be easily obtained in the market, for example, ester acrylates, ether acrylates, urethane acrylates, epoxy acrylates, amino resin acrylates, acrylic resin acrylates, unsaturated polyesters. Etc. can be illustrated.

(Epoxy (meth) acrylate resin having carboxyl group)
Although it does not specifically limit as an epoxy (meth) acrylate resin which has a carboxyl group, The epoxy (meth) obtained by making the reaction material of an epoxy compound and unsaturated group containing monocarboxylic acid react with an acid anhydride. Acrylate compounds are suitable.

  Although it does not specifically limit as an epoxy compound, A bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a phenol novolac type epoxy compound, a cresol novolak type epoxy compound, an aliphatic epoxy compound, or Examples thereof include epoxy compounds such as bisphenolfluorene type epoxy compounds. These may be used alone or in combination of two or more.

  Examples of the unsaturated group-containing monocarboxylic acid include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, (meth) acryloyloxyethyl hexahydrophthalic acid, (Meth) acrylic acid dimer, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid and the like. Also, half-ester compounds that are reaction products of hydroxyl group-containing acrylates with saturated or unsaturated dibasic acid anhydrides, reaction products of unsaturated group-containing monoglycidyl ethers with saturated or unsaturated dibasic acid anhydrides. A half ester compound is also mentioned. These unsaturated group-containing monocarboxylic acids may be used alone or in combination of two or more.

  Examples of acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, Dibasic acid anhydrides such as methylenetetrahydrophthalic acid, chlorendic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl Aromatic polycarboxylic anhydrides such as ether tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, endobicyclo- [2 , 2,1] -Hept-5-ene-2,3-dica Polycarboxylic anhydride derivatives such as carbon anhydride, and the like. These may be used alone or in combination of two or more.

  The molecular weight of the epoxy (meth) acrylate compound having a carboxyl group thus obtained is not particularly limited, but is preferably 1000 to 40000, more preferably 2000 to 5000.

(B) Polyfunctional monomer Examples of the polyfunctional monomer in the present invention include di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol; di (meth) acrylate of polyalkylene glycol such as polyethylene glycol and polypropylene glycol. ) Acrylates; poly (meth) acrylates of polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. and their dicarboxylic acid modified products; polyesters, epoxy resins, urethane resins, alkyd resins , Oligo (meth) acrylates such as silicone resins and spirane resins; both ends such as hydroxypoly-1,3-butadiene at both ends, hydroxypolyisoprene at both ends, and hydroxypolycaprolactone at both ends Examples thereof include di (meth) acrylates of terminal hydroxylated polymers; tris (2- (meth) acryloyloxyethyl) phosphate and the like.

  Of these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products are preferable. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tris. Succinic acid modified products of (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable. The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The usage-amount of the polyfunctional monomer in this invention is 5-500 weight part normally with respect to 100 weight part of alkali-soluble resin, Preferably it is 20-300 weight part. In this case, if the amount of the polyfunctional monomer used is less than 5 parts by weight, the pattern strength and the smoothness of the pattern surface tend to decrease. There is a tendency that stains and film residues are likely to occur in regions other than the portion where the pattern is formed.

  In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer. Examples of such monofunctional monomers include carboxyl group-containing unsaturated monomers or other unsaturated monomers constituting alkali-soluble resins, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl. A methacrylate etc. can be mentioned. Among these monofunctional monomers, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, methoxy Triethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate and the like are preferable. The monofunctional monomers can be used alone or in admixture of two or more. The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 50% by weight or less, based on the total amount of the polyfunctional monomer and the monofunctional monomer.

(C) Photopolymerization initiator and sensitizer The negative photosensitive binder system is usually blended with a photopolymerization initiator having activity with respect to the wavelength of the light source used. The photopolymerization initiator is appropriately selected in consideration of the difference in the reaction format of the polymer having photopolymerization and the photopolymerization monomer (for example, radical polymerization and cationic polymerization) and the kind of each material, and is not particularly limited.

  Among these, when the photopolymerization property of the binder system is radical photopolymerization, one or more types are selected from the compound group represented by the following formula (1) as the photopolymerization initiator used in the present invention. It is preferable to use in.

（式中、Ｒ¹乃至Ｒ¹⁴は、それぞれ独立して水素、ヒドロキシル基、アミノ基、カルボキシル基、ハロゲン、ケトン基、芳香族基、又は脂肪族基のいずれかである。但し、前記芳香族基及び脂肪族基は、分岐構造及び脂環式構造から選ばれる構造を含んでいても良く、基の途中にエーテル結合、エステル結合、アミノ結合、アミド結合、チオエーテル結合、不飽和結合から選ばれる１種以上を含んでいても良く、基の末端にヒドロキシル基、アミノ基、カルボキシル基、ハロゲン、カルボニル基、芳香族基から選ばれる１種以上を含んでいても良い。）

(In the formula, R ^{1 to} R ¹⁴ are each independently hydrogen, hydroxyl group, amino group, carboxyl group, halogen, ketone group, aromatic group, or aliphatic group. The group and the aliphatic group may include a structure selected from a branched structure and an alicyclic structure, and are selected from an ether bond, an ester bond, an amino bond, an amide bond, a thioether bond, and an unsaturated bond in the middle of the group. One or more kinds may be contained, and one or more kinds selected from a hydroxyl group, an amino group, a carboxyl group, a halogen, a carbonyl group, and an aromatic group may be contained at the terminal of the group.

By substituting halogen at one or two or more arbitrary positions of R ^{1 to} R ¹⁴ , it is possible to increase the cleavage reactivity of the compound of formula (1) at the time of light irradiation, and further improve the sensitivity. be able to. Examples of halogen include Br and Cl.

Moreover, the compound of Formula (1) is substituted by substituting a hydroxyl group, an amino group, a carboxyl group, a ketone group, an aromatic group, or an aliphatic group at one or two or more arbitrary positions of R ^{1 to} R ¹⁴ . The absorption spectrum can be changed, and the absorption wavelength characteristic can be adjusted according to the irradiation wavelength. Examples of the ketone group include those containing an alkyl group having 1 to 10 carbon atoms or an aromatic group having 5 to 14 carbon atoms. These alkyl groups and aromatic groups may have a substituent, or may have a structure other than hydrocarbon in the middle of the group.

  As the aromatic group, an aromatic group having 5 to 20 carbon atoms is preferable. For example, in addition to an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, a group containing a heteroatom other than a hydrocarbon such as a pyridyl group. Also mentioned.

  As the aliphatic group, an aliphatic group having 1 to 10 carbon atoms is preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl. In addition to an aliphatic hydrocarbon group such as a group, an alkyl group such as an n-hexyl group, and an unsaturated hydrocarbon group such as an alkenyl group, a group containing a hetero atom other than a hydrocarbon is also included.

As a photoinitiator represented by Formula (1), the following are mentioned, for example.
Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-ethyl-6- (4-methylbenzoyl) ) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O -Acetyloxime), ethanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-rubazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-ethyl- 6- (2,6-Dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-ethyl-6- (2,4,6-trimethylben) Yl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- ( O-acetyloxime), ethanone 1- [9-ethyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-ethyl-6 -(6-Ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3 -Yl]-1- (O-acetyloxime), ethanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyl) Oxime) ethanone 1- [9-ethyl-6- (2,4,6-ethylbenzoyl) -9H- carbazoyl-3-yl]-1-(O-acetyl oxime),

  Ethanone 1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-methyl-6- (4-methylbenzoyl) ) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O -Acetyloxime), ethanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-methyl- 6- (2,6-Dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-methyl-6- (2,4,6-trimethylbenzo) ) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-methyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- ( O-acetyloxime), ethanone 1- [9-methyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-methyl-6 -(6-Ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3 -Yl] -1- (O-acetyloxime), ethanone 1- [9-methyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxy) Shim), ethanone 1- [9-methyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),

  Ethanone 1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-propyl-6- (4-methylbenzoyl) ) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O -Acetyloxime), ethanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-propyl- 6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-propyl-6- (2,4,6-trime Tilbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-propyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-propyl- 6- (6-Ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), ethanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl- 3-yl] -1- (O-acetyloxime), ethanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl]- - (O-acetyl oxime) ethanone 1- [9-propyl-6- (2,4,6-ethylbenzoyl) -9H- carbazoyl-3-yl]-1-(O-acetyl oxime),

  Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-ethyl-6- ( 4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-ethyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1 [9-ethyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-ethyl-6 (2-Ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-ethyl-6- (4-ethylbenzoyl) -9H-carbazoyl- 3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- ( 1-propanone) oxime], ethanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1 -[9 -Ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-ethyl-6- (2,4 , 6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazoyl- 3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-methyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- ( 1-propanone) oxime], ethanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [ 9-Me Ru-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-methyl-6- (2,6- Dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-methyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl -3-yl] -1- [O- (1-propanone) oxime],

  Ethanone 1- [9-methyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-methyl-6- ( 4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-methyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1 -[9-methyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-propyl-6 -(2-Methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-propyl-6- (4-methylbenzoyl) -9H-carbazoyl -3-yl] -l- [O- (1-propanone) oxime], ethanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], etano 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],

  Ethanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-propyl-6- ( 4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], ethanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], Thanone 1- [9-propyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], Ethanone 1- [9-ethyl -6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-ethyl-6- (4-methylbenzoyl) -9H -Carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [ O- (1-butanone) oxime], ethanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime] , Ethanon 1- [9-ethyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-ethyl-6- (2 , 4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H- Carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-ethyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O -(1-butanone) oxime], ethanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1 -[9-ethyl- -(2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-ethyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3- Yl] -1- [O- (1-butanone) oxime],

  Ethanone 1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-methyl-6- ( 4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-Me Ru-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-methyl-6- (2- Ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-methyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl ] -1- [O- (1-butanone) oxime], ethanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) ) Oxime], ethanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9 -Methyl-6- (2, 6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-methyl-6- (2,4,6-triethylbenzoyl) -9H -Carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [ O- (1-butanone) oxime], ethanone 1- [9-propyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-propyl-6- (2 , 4-Di Tilbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [ O- (1-butanone) oxime],

  Ethanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-propyl-6- ( 4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1 [9-propyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], ethanone 1- [9-ethyl-6 (2-Methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-ethyl-6- (4-methylbenzoyl) -9H-carbazoyl- 3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- ( 1-pentanone) oxime], ethanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1 -[9 -Ethyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-ethyl-6- (2,4 , 6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],

  Ethanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-ethyl-6- ( 4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1 [9-ethyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-methyl-6 (2-Methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-methyl-6- (4-methylbenzoyl) -9H-carbazoyl- 3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- ( 1-pentanone) oxime], ethanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1 -[9 -Methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-methyl-6- (2,4 , 6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],

  Ethanone 1- [9-methyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-methyl-6- ( 4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-methyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1 [9-methyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-propyl-6 (2-Methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-propyl-6- (4-methylbenzoyl) -9H-carbazoyl- 3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- ( 1-pentanone) oxime], ethanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-propyl-6 (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],

  Ethanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-propyl-6- ( 4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], ethanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], Thanone 1- [9-propyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-ethyl -6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-ethyl-6- (4-methylbenzoyl) -9H-carbazoyl-3 -Yl] -1- (O-acetyloxime), propanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1 -[9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-ethyl-6- (2 , 6-Dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-ethyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl- 3-yl] -1- (O-acetyloxime),

  Propanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-ethyl-6- (4-ethylbenzoyl) ) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O -Acetyloxime), propanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-ethyl- 6- (2,6-Diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-ethyl-6- (2,4,6-tri Tylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-methyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-methyl- 6- (6-Methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl- 3-yl] -1- (O-acetyloxime), propanone 1- [9-methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl]- 1- (O-acetyloxime), propanone 1- [9-methyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime),

  Propanone 1- [9-methyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-methyl-6- (4-ethylbenzoyl) ) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O -Acetyloxime), propanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-methyl- 6- (2,6-Diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-methyl-6- (2,4,6-tri Tilbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-propyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-propyl- 6- (6-Methylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl- 3-yl] -1- (O-acetyloxime), propanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl- -Yl] -1- (O-acetyloxime), propanone 1- [9-propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime ),

  Propanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-propyl-6- (4-ethylbenzoyl) ) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O -Acetyloxime), propanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-propyl- 6-2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-propyl-6- (2,4 6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- (O-acetyloxime), propanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl]- 1- [O- (1-propanone) oxime], propanone 1- [9-ethyl-6- (4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime ], Propanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-ethyl-6 -(2,4-Dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-ethyl-6- (2,6-dimethyl) Tylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-ethyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl -3-yl] -1- [O- (1-propanone) oxime],

  Propanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-ethyl-6- ( 4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-propanone) oxime], propanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], Ropanone 1- [9-ethyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-methyl -6- (2-Methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-methyl-6- (4-methylbenzoyl) -9H -Carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [ O- (1-propanone) oxime], propanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime , Propanone 1- [9-methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-methyl- 6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],

  Propanone 1- [9-methyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-methyl-6- ( 4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-propanone) oxime], propanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-methyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], Ropanone 1- [9-methyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-propyl -6- (2-Methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-propyl-6- (4-methylbenzoyl) -9H -Carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [ O- (1-propanone) oxime], propanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) Oxime], propanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9- Propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime],

  Propanone 1- [9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-propyl-6- ( 4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-propanone) oxime], propanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl]-1- [O- (1-propanone) oxime], propanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) o Sim], propanone 1- [9-propyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-propanone) oxime], propanone 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-ethyl-6- (4-methylbenzoyl) ) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl]- 1- [O- (1-butanone) oxime], propanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) ) Oki Sim], propanone 1- [9-ethyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9- Ethyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],

  Propanone 1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-ethyl-6- ( 4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-butanone) oxime], propanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone1- [9-ethyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-methyl- 6- (2-Methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-methyl-6- (4-methylbenzoyl) -9H- Carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O -(1-butanone) oxime], propanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], Propanone 1- 9-methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-methyl-6- (2, 4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-methyl-6- (2-ethylbenzoyl) -9H-carbazoyl -3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-methyl-6- (4-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1 [9- Tyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-methyl-6- (2,6- Diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-methyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl -3-yl] -1- [O- (1-butanone) oxime],

  Propanone 1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-propyl-6- ( 4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-butanone) oxime], propanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], Ropanone 1- [9-propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-propyl -6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-propyl-6- (4-ethylbenzoyl) -9H -Carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [ O- (1-butanone) oxime], propanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime , Propanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime], propanone 1- [9-propyl- 6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-butanone) oxime],

  Propanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-ethyl-6- ( 4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-ethyl-6- (6-methylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-ethyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-ethyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], Ropanone 1- [9-ethyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-ethyl -6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-ethyl-6- (4-ethylbenzoyl) -9H -Carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-ethyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [ O- (1-pentanone) oxime], propanone 1- [9-ethyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime , Propanone 1- [9-ethyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-ethyl- 6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],

  Propanone 1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-methyl-6- ( 4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-methyl-6- (6-methylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-methyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-methyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], Ropanone 1- [9-methyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-methyl -6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-methyl-6- (4-ethylbenzoyl) -9H -Carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-methyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [ O- (1-pentanone) oxime], propanone 1- [9-methyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime , Propanone 1- [9-methyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-methyl- 6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime],

  Propanone 1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-propyl-6- ( 4-methylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-propyl-6- (6-methylbenzoyl) -9H-carbazoyl-3 -Yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-propyl-6- (2,4-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-propyl-6- (2,6-dimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) o Sim], propanone 1- [9-propyl-6- (2,4,6-trimethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [ 9-propyl-6- (2-ethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-propyl-6- (4-ethylbenzoyl) ) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [9-propyl-6- (6-ethylbenzoyl) -9H-carbazoyl-3-yl]- 1- [O- (1-pentanone) oxime], propanone 1- [9-propyl-6- (2,4-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1- Ntanone) oxime], propanone 1- [9-propyl-6- (2,6-diethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime], propanone 1- [ 9-propyl-6- (2,4,6-triethylbenzoyl) -9H-carbazoyl-3-yl] -1- [O- (1-pentanone) oxime]

  The photopolymerization initiator represented by the formula (1) has high sensitivity, and by using this photopolymerization initiator, the sensitivity of the photosensitive binder system is dramatically improved, and thus the reaction proceeds efficiently. It can be sufficiently cured even with a smaller exposure amount than usual. In addition, because of the high sensitivity, the curing reaction proceeds sufficiently even when the titanium oxynitride particle concentration in the composition is high, the curing component concentration is small, or even in a deep position of the coating film where only a small amount of light reaches. Further, since the adhesion after curing to the substrate or the like which is the base becomes high, it is difficult for the pattern to flow during development, and a fine pattern shape can be formed accurately.

  Such an improvement in sensitivity is particularly remarkable in exposure in the presence of oxygen. Since the photopolymerization initiator represented by the formula (1) is less susceptible to reaction inhibition by oxygen, the polymerization reaction proceeds rapidly even in the presence of oxygen. Therefore, when a coating film is formed using the black resin composition for display elements of the present invention containing the photopolymerization initiator represented by the formula (1), an oxygen blocking film is applied to the coating film surface before exposure. There is no need to process or expose the coating film in a nitrogen atmosphere, and the complexity and cost of the process can be avoided.

In addition, reaction inhibition due to oxygen occurs strongly on the surface of the coating film in contact with oxygen, and thus tends to affect the surface shape of the pattern, particularly the sharpness of the edges. On the other hand, the use of the photopolymerization initiator of formula (1) in the black resin composition for display elements of the present invention makes it difficult for reaction inhibition by oxygen to occur, so the accuracy of the surface shape of the pattern is also improved.
Therefore, by using the photopolymerization initiator of the formula (1), the adhesion of the coating film to the base and the accuracy of the surface shape of the pattern are simultaneously improved. As a result, the color filter of the display device or the solid-state image sensor The fine and precise patterning properties required for the light shielding film can be obtained.

Of the compounds represented by the above formula (1), compounds in which R ^{2 to} R ¹¹ are hydrogen are preferable, and compounds in which R ^{2 to} R ¹¹ are hydrogen are R ¹ , R ¹² , R ^13. R ¹⁴ is preferably an aliphatic group having 1 to 3 carbon atoms.

Further, in the above formula (1), R ^{2 to} R ¹¹ are hydrogen, R ¹ is a methyl group, R ¹² is an ethyl group, R ¹³ is a methyl group, and R ¹⁴ is a methyl group. The compound represented efficiently generates radicals by irradiation with ultraviolet rays (330 to 370 nm as a guide) including i-line (365 nm) in the visible region, and gives high sensitivity to the photosensitive coloring composition.

  This is because the compound (2) has an absorption intensity of 330 to 370 nm such as 333 nm and 365 nm, compared with other initiators such as Irgacure 907 (manufactured by Ciba Specialty Chemicals) and the like that are often used in color filter applications. This is probably because the quantum yield is high and the quantum yield involved in the polymerization initiation reaction is high, so that the reaction can be advanced using light of 330 to 370 nm efficiently. As a photoinitiator of Formula (2), commercial items, such as CGI242 (made by Ciba Specialty Chemicals), can be used, for example.

  In the present invention, together with the compound represented by the above formula (1), other photopolymerization initiators having an action of inducing radical polymerization reaction by causing cleavage or hydrogen abstraction reaction when irradiated with light. , And may be used in combination as long as the above effects are not impaired. When two or more kinds of initiators are used in combination, it is preferable to use those having absorption with respect to the exposure wavelength to such an extent that each initiator is not significantly inhibited by reaction.

  Other photopolymerization initiators include, for example, compounds that generate free radicals by the energy of ultraviolet rays, and derivatives such as benzophenone derivatives such as benzoin and benzophenone or esters thereof; xanthone and thioxanthone derivatives; chlorosulfonyl, chloromethyl Halogenated compounds such as polynuclear aromatic compounds, chloromethyl heterocyclic compounds, chloromethylbenzophenones; triazines; fluorenones; haloalkanes; redox couples of photoreducing dyes and reducing agents; organic sulfur compounds; And preferably include ketone-based and biimidazole-based compounds.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis. (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetrakis (4- Ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2' -Bi Midazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2 ′ -Bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-bromo) Phenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5 5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxy) Carbonylpheny ) -1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-bi Imidazole, 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2 '-Bis (2,4,6-tribromophenyl) -4,4', 5,5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2 -Cyanophenyl) -4,4 ', 5.5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-cyanophenyl) -4,4', 5,5′-tetrakis (4-phenoxy Sicarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-methylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) -1,2'- Biimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis ( 2-methylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole,

  2,2′-bis (2-ethylphenyl) -4,4 ′, 5,5′-tetrakis (4-methoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-ethyl) Phenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-ethylphenyl) -4,4 ′, 5, 5'-tetrakis (4-phenoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-phenylphenyl) -4,4 ', 5,5'-tetrakis (4-methoxycarbonylphenyl) ) -1,2′-biimidazole, 2,2′-bis (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2'- (2-phenylphenyl) -4,4 ′, 5,5′-tetrakis (4-phenoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4 , 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dicyanophenyl) -4, 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, , 2′-bis (2,4,6-tricyanophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dimethyl) Phenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trimethylphenyl) -4,4 ′, 5,5 ′ -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-diethylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2, 2′-bis (2,4,6-triethylphenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-diphenylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bi (2,4,6-triphenylphenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

Specific examples include commercially available products such as biimidazole (manufactured by Kurokin Kasei Co., Ltd.) and CL2W2 (manufactured by Showa Denko KK).
These photopolymerization initiators may be used alone or in combination, and the content thereof is appropriately adjusted depending on the target system and is not particularly limited. For example, when at least the compound represented by the above formula (1) is used, 0.05 to 60 parts by weight, preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the negative photosensitive binder component. Parts by weight.

Moreover, in this invention, 1 or more types chosen from the group of a sensitizer and a hardening accelerator can also be further used together with the said photoinitiator as needed. Specific examples of the sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4- Dimethylaminobenzoate, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Etc. Specific examples of the curing accelerator include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-4, Examples include chain transfer agents such as 6-dimethylaminopyridine, 1-phenyl-5-mercapto-1H-tetrazole, and 3-mercapto-4-methyl-4H-1,2,4-triazole.
One or more selected from the group of these sensitizers and curing accelerators may be used alone or in combination, and the content thereof is not particularly limited, but with respect to a total weight of 100 parts by weight of the photopolymerization initiator. The amount is usually 5 to 70 parts by weight, preferably 10 to 50 parts by weight.

(Ii) Positive photosensitive binder system A positive photosensitive binder system containing a photocurable resin that can be polymerized and cured by light such as ultraviolet rays and electron beams comprises (A) an acid-decomposable resin and (B) a photoacid. It contains a generator.

  The acid-decomposable resin in the present invention is a resin having a group that can be converted into an alkali-soluble group (for example, a carboxyl group, a phenolic hydroxyl group, etc.) by contact with an acid. Resins in which -butoxycarbonyl group (-COOt-Bu), t-butoxycarbonylphenyloxycarbonyl group (-COOphCOOt-Bu), p- (t-butoxycarbonyloxy) phenyl group (-phOCOOOt-Bu), etc. are preferably bonded Can be used. More preferred specific examples include poly t-butyl (meth) acrylate, poly t-butoxycarbonylphenyl (meth) acrylate, poly p- (t-butoxycarbonyloxy) styrene and the like. These polymers may contain other monomer units.

  In the present invention, the photoacid generator is a compound that generates an acid upon irradiation with light, and one or more known compounds can be used as the photoacid generator. For example, onium halide-ion, BF4- ion, PF6- ion, AsF6- ion, SbF6- ion, CF3SO3- ion, etc., organic halogen compounds, naphthoquinone diazide sulfonic acid compounds, photosulfonic acid generating compounds, etc. are used. can do.

  Here, specific examples of the onium salt include those described in USP 4,069,055 and US 4,069,056. Specific examples of the diazonium salt include Photogr. Sci. Eng. , 18, 387 (1974), J.A. Macromol. Chem. Sci. , A21, 1695 (1984) and Polymer, 21, 423 (1980). Specific examples of iodonium salts include Macromolecules, 10, 1307 (1977), Chem. & Eng. NEWS. , Nov. 28, 31 (1988) and European Patent 0104143. Specific examples of sulfonium salts include Polymer J. et al. , 17, 73 (1985), Polymer Bull. 14, 279 (1985), J. Am. Polymer Sci. 17, 977 (1979), J. MoI. Org. Chem. 43, 3055 (1978), J. Am. Org. Chem. , 50, 4360 (1985), JP-A 57-18723, JP-A 56-8428, USP 4760013, USP 4139655, USP 4734444 and European Patent 0297433. Things can be mentioned. Specific examples of the phosphonium salt include those described in USP 4069055 specification, USP 4069056 specification and Macromolecules, 17, 2469 (1984). Specific examples of the selenium salt include those described in Macromolecules, 10, 1307 (1977). Specific examples of arsonium salts include Proc. Conf. Rad. Curing ASIA P478 Tokyo. Oct. (1988).

  Examples of the organic halogen compounds that generate an acid upon irradiation with light include phenyltrimethylsulfone compounds described in JP-B No. 46-4605, JP-B No. 48-36281, JP-A No. 53-133428, JP-A No. A halomethyl-S-triazine compound described in JP-A-60-105667 or JP-A-60-239736, Angew. Physik. Chem. 24.381 (1918), J.A. Phys. Chem. 66, 2449 (1962), JP 54-74728, JP 55-77742, JP 59-148784, JP 60-3626, JP 60-138539. And halomethioxadiazole compounds described in JP-A-60-239473.

  Examples of the photosulfonic acid generating compound include ester compounds of nitrobenzyl alcohol and arylsulfonic acid described in Macromolecules, 21, 2001 (1988) or JP-A No. 64-18143, European Patent No. 0044155 or No. 099672. Ester compound of oxime and aryl sulfonic acid described in the specification, ester compound of N-hydroxyamide or imide and sulfonic acid described in US Pat. No. 4,258,121 or US Pat. No. 4,618,564, European Patent No. 84515 or 199672 And ester compounds of benzoin and sulfonic acid described in the specification.

  Among these photoacid generators, organic halogen compounds, particularly halomethyl-S-triazine compounds, halomethyloxadiazole compounds, and photosulfonic acid generator compounds come into contact with an acid to produce an alkali-soluble group (for example, a carboxyl group, a phenol group). A group that can be converted into a hydroxyl group, for example, a t-butoxycarbonyl group or a t-butoxycarbonyloxyphenyl group, which can be efficiently decomposed.

  These acid generators may be used alone or in combination, and if the content is too small relative to the acid-decomposable resin, the amount of acid generated is small, and the acid-decomposable resin is sufficiently alkali-soluble. If the amount is too large, an unfavorable phenomenon in developability may occur. Therefore, it is preferably 0.05 to 15 parts by weight, more preferably 3 parts by weight based on 100 parts by weight of the acid-decomposable resin. ~ 15 parts by weight.

  In addition, in order to improve photoacid generation efficiency and to increase the sensitivity of the photosensitive resin composition, a photoacid generator and a sensitizer can be used in combination. These can be selected as appropriate according to the pigment used.

  As such a sensitizer, a known sensitizer can be used. For example, anthracene, phenanthrene, perylene, pyrene, chrysene, 1,2-benzoanthracene, coronene, 1,6-diphenyl-1, 3,5-hexatriene, 1,1,4,4-tetraphenyl-1,3-butadiene, 2,3,4,5-tetraphenylfuran, 2,5-diphenylthiophene, thioxanthone, 2-chlorothioxanthone, Phenothiazine, 1,3-diphenylvirazoline, 1,3-diphenylisobenzofuran, xanthone, benzophenone, 4-hydroxybenzophenone, anthrone, ninhydrin, 9-fluorenone, nitropyrene, 2,4,7-trinitrofluorenone, indanone, phenone Nansraquinone, 7-methoxy-4-methyl Phosphorus, 3-keto - bis (7-diethylamino coumarin), fluoro Sen, eosin, may be mentioned rhodamine S and triphenyl pyrylium perchlorate and the like.

  The ratio of these sensitizers and photoacid generators is preferably 0.01 / 1 to 10/1, more preferably 0.1 / 1 to 5/1 in terms of molar ratio.

(2) Thermosetting binder system Examples of the thermosetting system include a ring opening addition reaction system such as an epoxy group and active hydrogen, a cyclic urea group and a hydroxyl group, or a polyimide precursor that heat-closes imidizes polyamic acid. A system or the like can be used.

  As the thermosetting binder system, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is preferably used, and a catalyst capable of promoting a thermosetting reaction may be added. An epoxy group is preferably used as the thermosetting functional group. In addition, a polymer having no polymerization reactivity as described above may be further used.

  As a compound having two or more thermosetting functional groups in one molecule, an epoxy compound having two or more epoxy groups in one molecule is usually used. An epoxy compound having two or more epoxy groups in one molecule is an epoxy compound having two or more, preferably 2 to 50, more preferably 2 to 20 epoxy groups in one molecule (referred to as an epoxy resin). Is included). The epoxy group should just be a structure which has an oxirane ring structure, for example, can show a glycidyl group, an oxyethylene group, an epoxycyclohexyl group, etc. Examples of the epoxy compound include known polyvalent epoxy compounds that can be cured by carboxylic acid. Examples of such an epoxy compound include the “Epoxy Resin Handbook” edited by Masaki Shinbo, published by Nikkan Kogyo Shimbun (Showa 62). These can be used widely.

  Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin , Fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, water Bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy Shi resin, glycidyl amine type epoxy resins, glyoxal type epoxy resins, alicyclic epoxy resins, and the like heterocyclic epoxy resin. More specifically, bisphenol A type novolak epoxy resins such as trade name Epicoat 157S70 (manufactured by Japan Epoxy Resin Co., Ltd.) and cresol novolac type epoxy resins such as trade name YDCN-701 (manufactured by Tohto Kasei Co., Ltd.) can be mentioned. .

  As an epoxy compound, a polymer having a relatively high molecular weight, which is usually used as a binder component in order to impart adhesion, heat resistance, and alkali resistance to a cured film (hereinafter sometimes referred to as “binder epoxy compound”), In order to increase the crosslinking density of the cured film or adjust the viscosity of the composition, the compound having a molecular weight smaller than that of the binder epoxy compound and having two or more epoxy groups in one molecule (hereinafter referred to as “polyfunctional epoxy compound”). May be used in combination.

  The average molecular weight of the binder epoxy compound is preferably 1,000 to 100,000, and particularly preferably 2,000 to 50,000, when expressed in terms of polystyrene-equivalent weight average molecular weight. If the molecular weight of the binder epoxy compound is too small, the physical properties such as strength and solvent resistance required for the cured resin layer as details of the color filter are likely to be insufficient, while the molecular weight is 100, If it is more than 000, the viscosity tends to increase, the uniformity during coating on the substrate is impaired, and a large distribution tends to occur in the film thickness.

  On the other hand, the weight average molecular weight in terms of polystyrene of the polyfunctional epoxy compound is preferably 4,000 or less, particularly preferably 3,000 or less, on condition that it is smaller than the binder epoxy compound combined therewith. In addition, a weight average molecular weight means the value calculated | required by polystyrene conversion using the gel permeation chromatography (For example, HLC-8029, Tosoh Corporation make) which used tetrahydrofuran as the developing liquid.

  The binder epoxy compound has a limit in the amount of epoxy that can be introduced into the copolymer molecule. When a polyfunctional epoxy compound having a relatively small molecular weight is added to the resin composition, the epoxy group is replenished in the composition, the reaction point concentration of the epoxy is increased, and the crosslinking density can be increased. The polyfunctional epoxy compound can be appropriately selected from the polyvalent epoxy compounds described above.

  Moreover, as a hardening | curing agent, polyhydric carboxylic acid anhydride or polyhydric carboxylic acid is used, for example. The polyvalent carboxylic acid anhydride and the polyvalent carboxylic acid can be used singly or in combination of two or more.

  When the thermosetting functional group is an epoxy group, the amount of the curing agent used in the present invention is usually in the range of 1 to 100 parts by weight per 100 parts by weight of the epoxy group-containing component (monomer and resin). The amount is preferably 5 to 50 parts by weight. When the blending amount of the curing agent is less than 1 part by weight, curing becomes insufficient and a tough coating film cannot be formed. Moreover, when the compounding quantity of a hardening | curing agent exceeds 100 weight part, while the adhesiveness with respect to the board | substrate of a coating film is inferior, a uniform and smooth coating film cannot be formed.

In order to improve the hardness and heat resistance of the cured resin layer, a catalyst capable of promoting a thermosetting reaction such as between acid and epoxy may be added to the thermosetting binder system of the present invention. As such a catalyst, a thermal latent catalyst that exhibits activity during heat curing can be used.
The heat-latent catalyst exhibits catalytic activity when heated, accelerates the curing reaction and gives good properties to the cured product, and is added as necessary. The thermal latent catalyst is preferably one that exhibits acid catalytic activity at a temperature of 60 ° C. or higher. As such, a compound obtained by neutralizing a protonic acid with a Lewis base, a compound obtained by neutralizing a Lewis acid with a Lewis base, Lewis Examples thereof include a mixture of an acid and a trialkyl phosphate, sulfonic acid esters, onium compounds, and the like, and various compounds described in JP-A-4-218561 can be used.

  The total amount of the curable binder system is preferably 15 to 67 parts by weight, preferably 25 to 62 parts by weight, based on 100 parts by weight of the solid content of the black resin composition for display elements.

<Other ingredients>
(solvent)
The black resin composition for display elements according to the present invention usually contains a solvent for imparting coating properties.
Examples of the solvent used in the present invention include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol; cellosolv solvents such as methoxy alcohol and ethoxy alcohol; methoxyethoxyethanol, ethoxyethoxyethanol, and the like. Carbitol solvents such as ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, and ethyl lactate; ketone solvents such as acetone, methyl isobutyl ketone, and cyclohexanone; methoxyethyl acetate, methoxypropyl acetate Cellosolve acetate solvents such as methoxybutyl acetate, ethoxyethyl acetate, ethyl cellosolve acetate; methoxyethoxyethyl acetate, Carbitol acetate solvents such as toxiethoxyethyl acetate; ether solvents such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and tetrahydrofuran; non-solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone Protic amide solvent; Lactone solvent such as γ-butyrolactone; Unsaturated hydrocarbon solvent such as benzene, toluene, xylene, naphthalene; Saturated hydrocarbon solvent such as N-heptane, N-hexane, N-octane, etc. An organic solvent is mentioned. Among these solvents, cellosolve acetate solvents such as methoxyethyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate and ethoxyethoxyethyl acetate; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene Ether solvents such as glycol diethyl ether; ester solvents such as methyl methoxypropionate, ethyl ethoxypropionate and ethyl lactate are preferably used. More preferably, MBA (acetate-3-methoxy _{butyl, CH 3 CH (OCH 3)} CH 2 CH 2 OCOCH 3), PGMEA ( propylene glycol monomethyl ether _{acetate, CH 3 OCH 2 CH (CH} 3) OCOCH 3), DMDG (Diethylene glycol dimethyl ether, H ₃ COC ₂ H ₄ OCH ₃ ), diethylene glycol methyl ethyl ether, or a mixture thereof can be used.

  These solvents may be used alone or in combination of two or more. In the present invention, the solid content concentration of the black resin composition for display elements is adjusted to 5 to 70% by weight using a solvent.

  If necessary, the black resin composition for display elements according to the present invention may further include a dispersant, a surfactant, an adhesion promoter, an ultraviolet blocker, an ultraviolet absorber, a surface conditioner (leveling agent), or others. These ingredients may be blended.

(Pigment dispersant)
The pigment dispersant is blended in the resin composition as necessary in order to favorably disperse a pigment such as titanium oxynitride. Examples of the pigment dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, polymer surfactants (polymer dispersants) as exemplified below are preferable.

  The dispersant is blended as necessary in order to disperse the colorant satisfactorily. Specific examples include amide compounds such as nonanamide, decanamide, dodecanamide, N-dodecylhexadecanamide, N-octadecylpropioamide, N, N-dimethyldodecanamide and N, N-dihexylacetamide, diethylamine, diheptylamine, Amine compounds such as dibutylhexadecylamine, N, N, N ′, N′-tetramethylmethanamine, triethylamine, tributylamine and trioctylamine, monoethanolamine, diethanolamine, triethanolamine, N, N, N ′, N ′-(tetrahydroxyethyl) -1,2-diaminoethane, N, N, N′-tri (hydroxyethyl) -1,2-diaminoethane, N, N, N ′, N′-tetra (hydroxyethyl) Polyoxyethylene) -1,2-diaminoethane, 1 , 4-bis (2-hydroxyethyl) piperazine and amines having a hydroxy group such as 1- (2-hydroxyethyl) piperazine, and the like, and other compounds such as nipecotamide, isonipecotamide, and nicotinamide are listed. be able to.

  Furthermore, (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts, (partial) ammonium salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid ( (Part) Alkylamine salts; (Co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphorus Acid salts; amides obtained by the reaction of poly (lower alkylene imine) and free carboxyl group-containing polyester, salts thereof, and the like can be mentioned.

Further, as a commercially available dispersant, Disperbyk-101, -116, -130, -140, -160, -161, -162, -163, -164, -166, and- 167, same-168, same-170, same-171, same-174, same-182, same-2000, same-2001, same--2050 (above as the Big Chemie Japan Co., Ltd. product), EFKA-4046, same. -4047 (above, manufactured by EFAK CHEMICALS), Solsperse 12000, 13240, 13940, 17000, 20000, 24000GR, 24000SC, 27000, 28000, 32000, 33500, 33500, 35200, 37500 (above, manufactured by Nippon Lubrizol Co., Ltd.), Azisper PB711, 8 21 and 822 (above, manufactured by Ajinomoto Fine Techno Co., Ltd.).
The pigment dispersant may be used alone or in combination, and the content thereof is appropriately adjusted because it varies greatly depending on the curable binder system and the pigment concentration, and is not particularly limited. For example, it is preferable to mix | blend in the ratio of 3-33 weight part with respect to 100 weight part of pigments in the black resin composition for display elements, and also 5-30 weight part.

(Pigment)
If necessary, other pigments may be used for the black resin composition for display elements of the present invention. Specifically, carbon black, Cu—Fe—Mn oxide, synthetic iron black, anthraquinone, phthalocyanine, benzimidazolone, quinacridone, azo chelate, azo, isoindolinone, pyranthrone, indium Examples include pigments such as danslon, anthrapyrimidine, dibromoanthanthrone, flavanthrone, perylene, perinone, quinophthalone, thioindigo, and dioxazine, which can be used alone or in combination. .
Especially, it is preferable to contain 3-20 weight% of carbon black with respect to the whole pigment containing the said titanium oxynitride, and also containing 5-15 weight%. In such a case, the black resin composition for display elements can effectively reduce colored reflected light (yellowish red) while achieving high optical density with a thin film while maintaining patternability. it can. Although it does not specifically limit as carbon black used together, What has an average particle diameter of 20 nm-50 nm is used suitably.
Examples of commercially available carbon black include # 260, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 45L, # 47, # 50, # 52 manufactured by Mitsubishi Chemical Corporation. MA7, MA8, MA11, MA100, MA100R, MA100S, MA230, manufactured by DEGUSSA Printex A, Printex L, Printex P, Printex 30, Printex 35, Printex 40, Printex 45, Printex 55, Printex 60, Printex 300, Printex 350 , Special Black 4, Special Black 350, Special Black 550, Columbian Carbon Japan Co., Ltd. Raven1255, Raven1250, Raven1200, Raven1080 ULTRA, Raven1060 ULTRA, Raven1040, Raven1035, Raven1020 and the like.
For reducing the colored reflected light, for example, a 0.8 μm-thick coating film is formed on a glass substrate using the black resin composition for display elements of the present invention having a P / V ratio of 1.8. The reflection spectrum of visible light from the glass substrate side can be measured and evaluated in the wavelength range of 400 to 800 nm using an ultraviolet-visible spectrophotometer (UV-2550, manufactured by Shimadzu Corporation) at an incident angle of 5 °.

(Surfactant)
Furthermore, when various surfactants are used in combination, the dispersion stability can be improved. Examples of the surfactant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. For example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether Examples include alkylphenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; and polyethyleneimines.

  The product names of the surfactants are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (Dainippon Ink Chemical Co., Ltd.) )), Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), and the like.

(Other)
a) Adhesion promoter: For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and the like.
b) Ultraviolet absorber: For example, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.
c) Leveling agent: For example, commercially available silicon-based, polyoxyalkylene-based, fatty acid ester-based, special acrylic-based polymer, and the like.

  In the black resin composition for display elements of the present invention, the weight ratio (P / V) of the pigment (P) containing the titanium oxynitride particles and the solid content (V) other than the pigment is 0.1 to 5. It is preferably 0, more preferably 0.5 to 3.0, and particularly preferably 0.6 to 2.6.

<Method for producing black resin composition for display element>
The black resin composition for a display element of the present invention is mixed with a titanium oxide and a binder system, if necessary, together with other blending components and mixed in a solvent that is a single solvent or a mixed solvent, and solidified by a known dispersion method. It can be produced by dissolving or dispersing the components.
However, in the above method, a large amount of pigment such as titanium oxynitrogen may not be sufficiently dispersed in the solvent. Therefore, a pigment dispersion liquid is prepared by mixing a pigment such as titanium oxynitride and a dispersant in a solvent as required, and dispersing the pigment dispersion. On the other hand, other components such as a binder system are mixed, dispersed or dissolved in the solvent. It is preferable to prepare a binder liquid. And the black resin composition for display elements excellent in pigment dispersibility, such as titanium oxynitrogen, is easily obtained by mixing the obtained pigment dispersion liquid and binder liquid, and performing a dispersion process as needed.

  If the pigment dispersion is not prepared in advance, after the pigment such as titanium oxynitrogen particles is dispersed in the solvent by first adding a pigment such as titanium oxynitrogen, and if necessary, thoroughly mixing and stirring. In addition, by adding and mixing the remaining components including the binder system, the dispersibility is not hindered by other compounding components in the pigment dispersion step such as titanium oxynitride, and the stability is also excellent.

  Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibration ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, and more preferably 0.10 to 1.0 mm.

<Resin coating film for display element>
When the black resin composition for a display element thus obtained is a photosensitive resin composition and has an alkali developability, the composition is applied to a support to form a coating film and dried. Then, after changing the solubility between the exposed part and the unexposed part, such as selectively curing part of the coating by irradiating the coating with light in a predetermined pattern, By developing, a black coating film having a predetermined pattern is obtained.

  Further, when the obtained black resin composition for a display element is a thermosetting resin composition or does not have alkali developability, the composition is applied to a predetermined region of the support by an inkjet method, thermal transfer, or the like. After selectively attaching, a black coating film having a predetermined pattern is obtained by curing by heating or light irradiation.

As a light beam used for the curing reaction, a light beam having a wavelength that causes a reaction of the photosensitive binder system is appropriately selected and used from radiation such as ultraviolet rays and ionizing radiation or visible light. Irradiation energy required for curing is typically, 10 to 500 mJ / m ² approximately. In the exposure step, a predetermined position of the coating film can be selectively exposed and cured by irradiating the surface of the coating film with laser light or irradiating light through a mask.

  Moreover, although the conditions of heat-curing differ with binder systems, it is normally dried at 50-200 degreeC using a vacuum dryer, oven, a hotplate, or another apparatus to which heat is given, and then 120-400 degreeC. Heat cure at a moderate temperature.

  Since the resin coating film for a display element formed using the black resin composition according to the present invention can achieve a high optical density even if the content of titanium oxynitride is relatively small, a sufficient optical density can be achieved compared to the conventional case. It can be realized with a thin film, and a higher optical density can be realized with a conventional film thickness.

Specifically, the optical density (OD value) of the resin coating film can obtain an OD value of 4.0 or more at a film thickness of 0.7 μm. Here, the film thickness in the present invention is an average film thickness and can be measured using, for example, a stylus type film thickness measuring machine (manufactured by KLA TENCOR).
Here, the optical density (OD value) is obtained from the stimulus value Y in the XYZ color system by the following equation.
OD value = -log ₁₀ (Y / 100)

  The black resin composition according to the present invention can be used to form various black coating films, but has a merit capable of patterning details in particular. It is suitable for forming a light shielding layer (black matrix). Moreover, it can be used suitably also for optical element members, such as a color filter, used for image input devices, such as a solid-state image sensor.

<Display element member>
The display element member according to the present invention includes a light shielding layer formed using the black resin composition for a display element according to the present invention.
The display element member according to the present invention may be a thin film light-shielding layer having a sufficient optical density by including a light-shielding layer formed using the black resin composition for display elements according to the present invention. Therefore, it is possible to cope with a thin film and high performance optical element, and further, the step of the pixel portion can be reduced, so that display unevenness can be reduced.

FIG. 3 is a longitudinal sectional view showing an example of the color filter for display device (color filter 103) belonging to the display element member according to the present invention.
The color filter 103 covers the light shielding layer 6 formed in a predetermined pattern on the transparent substrate 5, the colored layer 7 (7R, 7G, 7B) formed in a predetermined pattern on the light shielding layer, and the colored layer. The protective film 8 formed in this way is provided. A transparent electrode 9 for driving liquid crystal may be formed on the protective film as necessary. An alignment film 10 is formed on the innermost surface of the color filter 103, in this case on the transparent electrode.

  The columnar spacer 12 has a shape of a convex spacer, and is formed at a plurality of predetermined positions on the transparent electrode 9 in accordance with a region (non-display region) where the light shielding layer 6 is formed. The columnar spacer 12 is formed on the transparent electrode 9, the colored layer 7, or the protective film 8. In the color filter 103, columnar spacers are formed in a sea-island shape on the protective film 8 via the transparent electrode 9, but the protective film 8 and the columnar spacer 12 are integrally formed and transparent so as to cover it. An electrode layer may be formed.

  The transparent substrate 5 of the color filter 101 is a transparent rigid material having no flexibility such as quartz glass, Pyrex (registered trademark) glass, or synthetic quartz plate, or a flexibility such as a transparent resin film or an optical resin plate. A transparent flexible material having the following can be used. Among them, Corning 1737 glass is a material having a small coefficient of thermal expansion, excellent in dimensional stability and workability in high-temperature heat treatment, and is an alkali-free glass containing no alkali component in the glass. Suitable for filters.

  The light shielding layer 6 is provided so as to surround between the colored layers 7R, 7G, and 7B and the outside of the colored layer forming region in order to improve the contrast of the display image. In the present invention, the light shielding layer 6 is formed using the black resin composition for display elements according to the present invention, which contains light shielding particles.

  When the black resin composition for display elements according to the present invention is a photosensitive resin composition and has alkali developability, first, the black resin composition according to the present invention is applied onto the transparent substrate 5. The light-shielding layer 6 is formed by drying as necessary to form a photosensitive coating film, exposing and developing the coating film through a photomask for the light-shielding layer, and performing heat treatment as necessary. can do.

  On the other hand, when the black resin composition for display elements according to the present invention is a thermosetting resin composition or does not have alkali developability, the black resin composition according to the present invention is applied to the transparent substrate 5. The light shielding layer 6 can be formed by selectively adhering to a predetermined region by an ink jet method, thermal transfer or the like, and then curing by heating or light irradiation.

  The thickness of the light shielding layer varies depending on the applicable display element member, and is about 0.5 to 2.5 μm. In the present invention, the thickness of the light shielding layer can be reduced by using the black resin composition according to the present invention. Since sufficient light-shielding properties can be obtained, the thickness of the light-shielding layer can be made thinner than before, and can be 0.3 to 1.0 μm. In the present invention, the film thickness when about 1.5 μm is conventionally required can be about 0.7 μm.

  The colored layer 7 includes a red pattern, a green pattern, and a blue pattern arranged in a desired form such as a mosaic type, a stripe type, a triangle type, and a four-pixel arrangement type, thereby forming a display region. The colored layer can be formed by a known method such as a pigment dispersion method, a dyeing method, a printing method, or an electrodeposition method, and among them, a pigment dispersion using a curable resin composition containing a colorant such as a pigment. Preferably, it is formed by the method.

  In the case of the pigment dispersion method, first, colorants such as pigments are dispersed in the curable resin composition to prepare photocurable colored resin compositions for red, green, and blue, respectively. Next, a certain color, for example, a photocurable red resin composition is applied on the transparent substrate 5 by a known method such as spin coating so as to cover the light shielding layer 6 to form a photocurable red resin layer, The red colored layer 7R is formed by performing exposure through a photomask for red pattern, alkali development, and heat curing in a clean oven or the like. Thereafter, green and blue photocurable colored resin compositions are sequentially used to pattern each color in the same manner to form a green colored layer 7G and a blue colored layer 7B.

  The thickness of the colored layer is usually about 0.5 to 2.5 μm. In the present invention, since the film thickness of the light shielding layer 6 can be reduced, the step of the colored layer as shown in FIG. 2 can be reduced. For example, the step 22 between the surface 20 of the colored layer and the apex 21 of the portion riding on the light shielding layer can be realized to be 0.05 to 0.30 μm. As a result of the reduction in the level difference, a display element member that can reduce display unevenness of the display element can be obtained.

  The protective film 8 is provided to flatten the surface of the color filter and prevent the components contained in the colored layer 7 from eluting into the liquid crystal layer. The protective film 8 covers the light-shielding layer 6 and the colored layer 7 with a known negative photocurable transparent resin composition or thermosetting transparent resin composition by a method such as spin coater, roll coater, spraying, printing, or the like. And can be formed by curing with light or heat.

In the present invention, since the step of the colored layer can be reduced as described above, a display element member with reduced display unevenness can be obtained without providing a protective film for planarization. The protective film may not be formed.
When forming the protective film, the thickness of the protective film is set in consideration of the light transmittance of the resin composition, the surface state of the color filter, and the like, and is, for example, about 0.1 to 2.0 μm. When using a spin coater, the number of revolutions is set within a range of 500 to 1500 revolutions / minute.

The transparent electrode film 9 on the protective film is made of indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), etc., and alloys thereof, such as sputtering, vacuum deposition, CVD, etc. It is formed by a general method, and is formed into a predetermined pattern by etching using a photoresist or using a jig as necessary. The thickness of the transparent electrode can be about 20 to 500 nm, preferably about 100 to 300 nm.
A plurality of convex spacers are provided in a non-display area on the substrate in order to maintain a cell gap when the color filter 103 is bonded to a liquid crystal driving side substrate such as a TFT array substrate. The shape and size of the convex spacer are not particularly limited as long as it can be selectively provided in a non-display region on the substrate and can maintain a predetermined cell gap over the entire substrate. When the columnar spacer 12 as shown in the figure is formed as the convex spacer, it has a certain height in the range of about 2 to 10 μm, and the protruding height (pattern thickness) is required for the liquid crystal layer. It can set suitably from thickness etc. Moreover, the thickness of the columnar spacer 12 can be appropriately set within a range of about 5 to 20 μm. Further, the formation density (density) of the columnar spacers 12 can be appropriately set in consideration of the thickness unevenness of the liquid crystal layer, the aperture ratio, the shape and material of the columnar spacers, for example, red, green and blue Necessary and sufficient spacer function is expressed at a ratio of one for each pixel. The shape of such a columnar spacer may be a columnar shape, and may be, for example, a columnar shape, a prismatic shape, a truncated cone shape, or the like.

  The convex spacer can be formed using a curable resin composition. That is, first, the coating liquid of the curable resin composition is applied directly on the transparent substrate by a method such as spin coater, roll coater, spray, printing, or through another layer such as a transparent electrode, and then dried. Then, a photocurable resin layer is formed. The rotational speed of the spin coater may be set within a range of 500 to 1500 revolutions / minute, as in the case of forming the protective film. Next, this resin layer is exposed through a photomask for convex spacers, and developed with a developer such as an alkaline solution to form a predetermined convex pattern. A convex spacer is formed by heat treatment (post-bake) or the like.

  The convex spacer can be provided directly on the color filter or indirectly through another layer. For example, a transparent electrode such as ITO or a protective film may be formed on the color filter, and a convex spacer may be formed thereon, or a protective film and a transparent electrode may be formed on the color filter in this order, and the transparent electrode A convex spacer may be formed on the top.

  The alignment film 10 is provided on the inner surface side of the color filter so as to cover the display portion including the colored layer 7 and the non-display portion including the light shielding layer 6 and the columnar spacer 12. The alignment film can be formed by applying a coating solution containing a resin such as a polyimide resin by a known method such as spin coating, drying, curing with heat or light as necessary, and then rubbing.

  When the color filter 103 (display side substrate) thus obtained and the TFT array substrate (liquid crystal drive side substrate) are made to face each other and the inner peripheral side edge portions of both the substrates are bonded with a sealant, the both substrates are separated by a predetermined distance. Bonding is performed with the cell gap maintained. An active matrix color liquid crystal display device belonging to the liquid crystal panel can be obtained by filling the liquid crystal in the gap between the substrates and sealing it.

<Production Example 1>
1. Coating titanium dioxide with silicon oxide 300 g of hydrous titanium dioxide is suspended in 1 liter of water as TiO ₂ to make a slurry, the pH of the slurry is adjusted to 10 with an aqueous sodium hydroxide solution, and the slurry temperature is then raised to 70 ° C. After warming, an aqueous sodium silicate solution was added dropwise for 2 hours. Subsequently, after heating the slurry temperature to 90 ° C., dilute sulfuric acid was added dropwise for 2 hours to neutralize the pH to 5, and the mixture was further maintained for 30 minutes. Thereafter, it was dehydrated, washed, and further fired at 850 ° C. for 5 hours in air to obtain titanium dioxide coated with dense silicon oxide (0.3% by weight as SiO ₂ ). The obtained titanium dioxide was anatase type.

2. Next, titanium dioxide coated with this silicon oxide was charged into a quartz tube having an inner diameter of 7.5 cm, and the quartz tube was heated to a temperature of 980 ° C. while ammonia gas was vented at a flow rate of 10 liters / minute. For 6 hours. Next, the obtained product is cooled to 100 ° C. under the same atmosphere, and further allowed to cool to room temperature in the air. The titanium oxynitride of the present invention whose composition formula is represented by TiN _0.95 O _0.20 · 0.01SiO ₂ (Sample A) was obtained.

<Production Example 2>
The hydrous titanium dioxide was baked in air at 850 ° C. for 5 hours to obtain titanium dioxide not coated with silicon oxide. The obtained titanium dioxide was a rutile type. This titanium dioxide not coated with silicon oxide was charged into a quartz tube having an inner diameter of 7.5 cm, and the quartz tube was heated at 980 ° C. for 3 hours while aeration of ammonia gas at a flow rate of 10 liters / minute. Next, the obtained product was cooled to 100 ° C. under the same atmosphere, and further allowed to cool to room temperature in the air. At this stage, in addition to the titanium oxynitride peak, a rutile-type titanium oxide peak was partially observed by X-ray diffraction. The product was again charged into a quartz tube having an inner diameter of 7.5 cm, and the quartz tube was heated at 980 ° C. for 3 hours while ventilating ammonia gas at a flow rate of 10 liters / minute, and then the resulting product was obtained. Was cooled to 100 ° C. under the same atmosphere, and further allowed to cool to room temperature in the air to obtain titanium oxynitride of the present invention (sample B) whose composition formula is represented by TiN _0.96 O _0.19 · 0SiO ₂ .

<Production Example 3>
In Production Example 1, the titanium oxynitride of the present invention represented by the compositional formula TiN _0.93 O _0.31 · 0.01SiO ₂ was prepared in the same manner as in Production Example 1 except that the heat reduction time at 980 ° C. was 3 hours. Sample C) was obtained.

<Production Example 4>
In Production Example 1, the titanium oxynitride of the present invention represented by the composition formula of TiN _0.89 O _0.48 · 0.01 SiO ₂ (sample) except that the heating and reducing conditions are 900 ° C. and 3 hours, as in Production Example 1. D) was obtained.

<Comparative Production Example 1>
In the same manner as in Production Example 1, titanium dioxide coated with silicon oxide (9% by weight as SiO ₂ ) was charged into a quartz tube having an inner diameter of 7.5 cm, and ammonia gas was vented at a flow rate of 10 liters / minute while quartz was introduced. The tube was heated at 900 ° C. for 3 hours. Next, the obtained product is cooled to 100 ° C. under the same atmosphere, and further allowed to cool to room temperature in the atmosphere. Titanium oxynitride whose composition formula is represented by TiN _0.88 O _0.64 · 0.11SiO ₂ (Sample E) Got.

<Comparative Production Example 2>
A commercially available titanium black (13M-C, manufactured by Mitsubishi Materials) whose composition formula is represented by TiN _0.75 O _0.58 · 0.001SiO ₂ was used as Comparative Sample F.

<Production Example 5>
1. Coating titanium dioxide with silicon oxide 300 g of hydrous titanium dioxide is suspended in 1 liter of water as TiO ₂ to make a slurry, the pH of the slurry is adjusted to 10 with an aqueous sodium hydroxide solution, and the slurry temperature is then raised to 70 ° C. After warming, an aqueous sodium silicate solution was added dropwise for 2 hours. Subsequently, after heating the slurry temperature to 90 ° C., dilute sulfuric acid was added dropwise for 2 hours to neutralize the pH to 5, and the mixture was further maintained for 30 minutes. Thereafter, it was dehydrated, washed, and further fired at 850 ° C. for 5 hours in air to obtain titanium dioxide coated with dense silicon oxide (0.3% by weight as SiO ₂ ). The obtained titanium dioxide was anatase type.
2. Next, titanium dioxide coated with this silicon oxide was charged into a SUS310 tube having an inner diameter of 25.5 cm, and the SUS310 tube was heated to a temperature of 980 ° C. while aeration of ammonia gas at a flow rate of 265 liters / minute. For 3 hours. Next, the obtained product was cooled to 100 ° C. under the same atmosphere, and further allowed to cool to room temperature in the air to obtain titanium oxynitride of the present invention (sample G) having a nitrogen content of 20.0% by weight. It was.

<Production Example 6>
27.5 g of titanium oxynitride (sample G) obtained in Production Example 5, 64 ml of water and 161.8 g of 0.5 mmφ zircon beads were charged in a glass bottle and pulverized with a paint conditioner (# 5110 model manufactured by Red Devil). Thereafter, the zircon beads were removed to obtain a wet pulverized slurry. The concentration of the obtained wet pulverized slurry was adjusted to 250 g / liter with pure water, the pH was adjusted to 7.0 with sulfuric acid, 0.55 g of γ-glycidoxypropyltrimethoxysilane was added at room temperature, and 80 After holding for 80 minutes, the temperature was raised to 80 ° C., stirred for 2 hours, adjusted to pH 2.5, dehydrated, washed, dried, and surface treated with 2% by weight of γ-glycidoxypropyltrimethoxysilane. Titanium oxynitride (Sample H) was obtained.

<Production Example 7>
27.5 g of titanium oxynitride (sample G) obtained in Production Example 5, 64 ml of water and 161.8 g of 0.5 mmφ zircon beads were charged in a glass bottle and pulverized with a paint conditioner (# 5110 model manufactured by Red Devil). Thereafter, the zircon beads were removed to obtain a wet pulverized slurry. The concentration of the obtained wet pulverized slurry was adjusted to 250 g / liter with pure water, 0.55 g of isopropyltri (N-amidoethylaminoethyl) titanate was added at room temperature, held for 20 minutes, dehydrated, washed, Dried to obtain titanium oxynitride (sample I) surface-treated with 2% by weight of isopropyltri (N-amidoethylaminoethyl) titanate.

<Production Example 8>
27.5 g of titanium oxynitride (sample G) obtained in Production Example 5, 64 ml of water and 161.8 g of 0.5 mmφ zircon beads were charged in a glass bottle and pulverized with a paint conditioner (# 5110 model manufactured by Red Devil). Thereafter, the zircon beads were removed to obtain a wet pulverized slurry. The concentration of the obtained wet pulverized slurry was adjusted to 250 g / liter with pure water, and a mixed solution of 0.55 g of isopropyltris (dioctyl pyrophosphate) titanate and 0.27 g of triethylamine was added at room temperature, and held for 20 minutes. Then, the pH was adjusted to 4.5 with sulfuric acid, dehydrated, washed, and dried to obtain titanium oxynitride (sample J) surface-treated with 2% by weight of isopropyltris (dioctyl pyrophosphate) titanate.

<Production Example 9>
27.5 g of titanium oxynitride (sample G) obtained in Production Example 5, 64 ml of water and 161.8 g of 0.5 mmφ zircon beads were charged in a glass bottle and pulverized with a paint conditioner (# 5110 model manufactured by Red Devil). Thereafter, the zircon beads were removed to obtain a wet pulverized slurry. The concentration of the obtained wet pulverized slurry was adjusted to 250 g / liter with pure water, heated to 70 ° C., adjusted to pH 10.5 with an aqueous sodium hydroxide solution, and the aqueous sodium aluminate solution was added dropwise over 20 minutes. Stir. Subsequently, dilute sulfuric acid was added dropwise for 20 minutes to neutralize the pH to 7.5, and the mixture was further maintained for 30 minutes. Thereafter, dehydration, washing, and drying were performed to obtain titanium oxynitride (sample K) surface-treated with 0.5% by weight of aluminum hydroxide.
The composition and characteristics of Samples A to F obtained in Production Examples and Comparative Production Examples are shown in Table 1-1, and the composition and characteristics of Samples G to K are shown in Table 1-2.

[Evaluation methods]
(1) Composition Content of titanium atom and silicon atom was analyzed by ICP emission spectroscopic analysis (GVM-1014, manufactured by Shimadzu Corporation). The oxygen atom content was analyzed by an inert gas carrier melting infrared absorption method (TC436AR manufactured by LECO), and the nitrogen atom content was analyzed by a carbon / hydrogen / nitrogen analyzer (vario EL III manufactured by Elemental). . X and n were calculated from these values. When silicon atoms were present, the silicon oxide content was calculated assuming that the silicon atoms were bonded to oxygen atoms to form silicon oxide SiO ₂ . Furthermore, the value obtained by subtracting the oxygen atom which becomes SiO ₂ by combining with the silicon atom from the analysis value of the oxygen atom was used as the value of the oxygen atom in TiNxOy, and y was calculated from the value. From these values, the composition formula, the O / N molar ratio, the O / N weight ratio, and x + y were determined.

(2) X-ray diffraction X-ray diffraction was measured by (RINT 2200, manufactured by Rigaku Corporation). The presence or absence of titanium dioxide was confirmed by the presence or absence of a titanium dioxide peak that appeared at 25 to 26 ° (A type) or 27 to 28 ° (R type) as 2θ. In addition, the reflection angle of the main peak of titanium oxynitride was determined. Further, from the half width of the main (first) peak between 40 ° and 45 ° as 2θ, the crystallite diameter constituting the titanium oxynitride particles was determined using the Schcrar's formula of the above-described formula 1.

(3) Lightness and hue As for the brightness and hue of titanium oxynitride, 1.5 g of a sample was placed in a glass round cell (Nippon Denshoku, part No. 1483), and a color difference meter (Nippon Denshoku) The color was measured with a Color Meter ZE2000 manufactured by the company, and the color was determined by the Lab color system.

(4) Reflectance measurement Using an ultraviolet-visible spectrophotometer (V-570 manufactured by JASCO Corporation), 0.3 g of titanium oxynitride powder is packed in a cylindrical cell (diameter 16 mm, manufactured by JASCO Corporation PSH-001 type) and visible. The reflection spectrum of light was measured.

(5) Particle diameter The sample was image | photographed with the electron microscope (Hitachi Ltd. H-7000), and the average particle diameter was measured.
(6) Specific surface area It measured with the simple BET method using the specific surface area measuring apparatus (Shimadzu Corporation Flow SorbII2300).
(7) Oxidation stability Since the nitrogen content decreases when titanium oxynitride is oxidized, a sample in which the nitrogen content of titanium oxynitride does not substantially decrease after standing for one month at room temperature has an oxidation stability of “ On the other hand, samples with a significantly reduced nitrogen content were judged as “bad”.

  4 to 9 show the visible light reflection spectra of Samples A to F obtained in Production Examples and Comparative Production Examples. Since the titanium oxynitride of the present invention has a high nitrogen content and a small crystallite diameter, the wavelength at which the minimum value of the visible light reflectance is shifted to the lower wavelength side compared to the comparative production example, and the visible light reflection It can be seen that the rate is high. Moreover, it turns out that the titanium oxynitride of this invention has a pigment characteristic comparable as a comparative manufacture example.

<Examples 1-15, Comparative Examples 1-3>
(Preparation of pigment dispersion)
A pigment, a pigment dispersant (product name Disperbyk 161 (containing 30% by weight of pigment dispersant in an organic solvent), manufactured by Big Chemie Japan) and an organic solvent were mixed in the composition shown in Table 2, and pre-dispersed with a disper. Further, this mixed solution was dispersed with a bead mill (trade name: Diamond Fine Mill MD-1 manufactured by Mitsubishi Heavy Industries, Ltd.) until a target dispersed particle size was obtained, and then the beads were removed to obtain dispersions 1 to 13. It was. The beads used were zirconia beads having a diameter of 0.10 mm, and the bead filling rate in the vessel was 70%. For the dispersed particle size, the pigment dispersion was diluted 1000 times with an organic solvent and the particle size distribution was measured using a Microtrac UPA particle size distribution meter (manufactured by Nikkiso Co., Ltd.). In Table 2, as carbon black sample L, Raven 1255 (average dispersed particle size 21 nm) manufactured by Colombian Carbon was used, and as sample M for carbon black, Raven 1040 (average dispersed particle size 28 nm) manufactured by Colombian Carbon. Was used.

(Preparation of binder solution)
Alkali-soluble resin, polyfunctional monomer, photopolymerization initiator, sensitizer, organic solvent, etc. are mixed in the composition shown in Table 3 and stirred until each component is completely dissolved to prepare binder solutions 1-4. did.

Alkali-soluble resin Epoxy (meth) acrylate resin: solid content 54%, weight average molecular weight 3600, acid value 114 mgKOH / g
・ Polyfunctional monomer TO1382 (manufactured by Toagosei Co., Ltd.)
・ Photopolymerization initiator CGI242 (Ciba Specialty Chemicals)
Biimidazole (manufactured by Kurokin Kasei Co., Ltd.)
Irgacure 369 (Ciba Specialty Chemicals)
Sensitizer 4,4-bis (diethylamino) benzophenone (hereinafter abbreviated as EAB: manufactured by Kanto Chemical Co., Inc.)
Organic solvent methoxybutyl acetate (hereinafter abbreviated as MBA: manufactured by Daicel Chemical Industries, Ltd.)
Cyclohexanone (Wako Pure Chemical Industries, Ltd.)

(Preparation of black resin composition for display element)
With the formulation shown in Table 4, the dispersion, the binder solution and the organic solvent were mixed, and after stirring for 2 hours, the mixture was filtered with a 0.2 μm filter to prepare resists 1 to 15 and comparative resists 1 to 3.

[Black resin composition evaluation 1 for display element]
The black resin compositions of Examples 1 to 15 and Comparative Examples 1 to 3 were subjected to an OD value of 4.0 using a spin coater on a 10 cm × 10 cm glass substrate (manufactured by Asahi Glass Co., Ltd.) having a thickness of 0.7 mm. And pre-baked on a 90 ° C. hot plate for 3 minutes to form a coating film. Next, the coating film was exposed through a photomask using an ultrahigh pressure mercury lamp. The substrate was developed with a 0.04 wt% aqueous potassium hydroxide solution (25 ° C.) for a predetermined time, further washed with pure water, and then dried. Thereafter, the substrate was post-baked for 30 minutes in a 230 ° C. clean oven to form a light-shielding layer in the region where the light-shielding portion was to be formed on the substrate. The photomask used has a pattern of lines and spaces: 1 to 100 μm.
About the obtained light shielding layer, each item shown below was evaluated. The evaluation results are shown in Table 5.

<OD value>
The OD value was determined from the stimulus value Y in the XYZ color system by the following formula using a microspectroscope OSP-SP200 (manufactured by OLYMPUS).
OD value = -log ₁₀ (Y / 100)

<Film thickness>
The film thickness was measured using a stylus type film thickness measuring machine (manufactured by KLA TENCOR).
<Sensitivity>
The minimum exposure amount at which a 20 μm line & space was in close contact was measured and evaluated according to the following criteria.
-: 10 m line adheres at 100 mJ / cm ² or less.
○: 20 μm line adheres at 100 mJ / cm ² or less.
-X: 100 mJ / cm < ² > or less, 20 [mu] m line does not adhere.

<Adhesion>
The minimum line width that was in close contact with the line and space of 1 μm to 50 μm without being flowed after the development process was measured and evaluated according to the following criteria.
-: A line of 10 μm or less adheres.
○: A line larger than 10 μm and 20 μm or less adheres.
X: Lines of 20 μm or less do not adhere.

[Black resin composition evaluation 2 for display elements]
For the black resin compositions of Example 11 and Example 15 and the black resin compositions of Example 14 and Example 15 in which the pigment of Example 11 was replaced with carbon black by 10% by weight of the total pigment, the reflected light of the coating film from the glass substrate side was measured. evaluated. About each black resin composition, it apply | coated so that OD value might be set to 4.0 with a spin coater on the glass substrate (Asahi Glass Co., Ltd.) of thickness 0.7mm and 10cm x 10cm, on a 90 degreeC hotplate. Pre-baking was performed for 3 minutes to form a coating film. Subsequently, the coating film was irradiated with an exposure amount of 60 mJ / cm ² using an ultrahigh pressure mercury lamp. About the obtained coating film, the reflection spectrum of visible light was measured in the wavelength range of 400-800 nm by the incident angle of 5 degrees using the ultraviolet visible spectrophotometer (Shimadzu Corporation UV-2550).
In FIG. 10, the visible light reflection spectrum of the coating film obtained from the black resin composition of Example 11, 14, and 15 is shown. Examples 14 and 15 using carbon black in an appropriate amount are effective in reducing colored reflected light (yellowish red) while exhibiting high optical density and good patternability in a thin film as in Example 11. It became clear that.

<Example A Color filter creation>
1. Formation of Black Matrix Using the black resin composition of Example 2 above on a 1.1 mm thick glass substrate (AL material manufactured by Asahi Glass Co., Ltd.), coating with a spin coater so that the OD value is 4.0. And dried at 90 ° C. for 3 minutes to form a light shielding layer (line width: 25 μm). The light shielding layer is exposed to a light shielding pattern with a super high pressure mercury lamp through a predetermined photomask, and then developed with a 0.5 wt% aqueous potassium hydroxide solution, and then the substrate is left in an atmosphere at 230 ° C. for 30 minutes. The black matrix was formed in the region where the light-shielding part was to be formed by heat treatment. At this time, the film thickness at the center of the light shielding portion was 0.7 μm.

2. Formation of colored layer (Preparation of photosensitive colored resin composition)
Each organic pigment, pigment dispersant, acrylic copolymer and organic solvent were mixed in the composition of the red pigment dispersion shown in Table 6, and pre-dispersed with a disper. Further, this mixed solution was dispersed with a bead mill (trade name: Diamond Fine Mill MD-1 manufactured by Mitsubishi Heavy Industries, Ltd.) until a target dispersed particle size was obtained, and then the beads were removed to obtain a pigment dispersion. The beads used were zirconia beads having a diameter of 0.30 mm, and the bead filling rate in the vessel was 70%. The dispersed particle diameter was measured by using a Microtrac UPA particle size distribution meter (manufactured by Nikkiso Co., Ltd.) after diluting the pigment dispersion 1000 times with an organic solvent. A green pigment dispersion and a blue pigment dispersion were prepared with the compositions shown in Table 6 by the same method.

Using the obtained red pigment dispersion, an alkali-soluble resin, a polyfunctional monomer, a photopolymerization initiator, and an organic solvent were mixed in the composition of the photosensitive red resin composition shown in Table 7, and after stirring for 2 hours, 0 was added. The mixture was filtered through a 2 μm filter to prepare a photosensitive red resin composition.
Green resin compositions and blue resin compositions having the compositions shown in Table 7 were prepared in the same manner.

Alkali-soluble resin Acrylic copolymer: benzyl methacrylate / methyl methacrylate / n-butyl methacrylate / methacrylic acid copolymer (solid content 54%, weight average molecular weight 11000, acid value 108 mgKOH / g)
・ Polyfunctional monomer TO1382 (manufactured by Toagosei Co., Ltd.)
-Photopolymerization initiator Irgacure 369 (Ciba Specialty Chemicals)
Organic solvent Propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA: manufactured by Daicel Chemical Industries, Ltd.)

Using the photosensitive red resin composition shown in Table 7, a red colored layer was formed so as to cover the opening part and the light shielding part partitioned by the above-described light shielding part from the end of the light shielding part by 7 μm. At this time, the thickness of the colored layer formed at the center of the opening section partitioned by the light shielding section was 2.0 μm. A green colored layer and a blue colored layer were formed by the same method to obtain a color filter.
The difference in film thickness between the maximum film thickness in the region where the light shielding layer and the colored layer were laminated and the film thickness of the colored layer formed at the center of the opening was defined as a step due to the film thickness of the light shielding layer.

<Comparative Example A Color filter creation>
-Formation of black matrix Using the black resin composition of Comparative Example 2 above on a 1.1 mm thick glass substrate (AL material manufactured by Asahi Glass Co., Ltd.), using a spin coater so that the OD value is 4.0. It was applied and dried at 90 ° C. for 3 minutes to form a light shielding layer (line width: 25 μm). The light shielding layer is exposed to a light shielding pattern with a super high pressure mercury lamp through a predetermined photomask, and then developed with a 0.5 wt% aqueous potassium hydroxide solution, and then the substrate is left in an atmosphere at 230 ° C. for 30 minutes. The black matrix was formed in the region where the light-shielding part was to be formed by heat treatment. The film thickness at the center of the light shielding part at this time was 1.2 μm.

-Formation of a colored layer It carried out similarly to Example A, formed the red colored layer, the green colored layer, and the blue colored layer, and obtained the color filter. The difference in film thickness between the maximum film thickness in the region where the light shielding layer and the colored layer were laminated and the film thickness of the colored layer formed at the center of the opening was defined as a step due to the film thickness of the light shielding layer.

[Evaluation result of step of colored layer]
Table 8 shows the thickness and OD value of the light shielding layer, the thickness of the colored layer, and the steps in each colored layer in the color filters prepared in Example A and Comparative Example A. From this result, by using the black resin composition for display elements of the present invention, a color filter having a high light-shielding property and suppressing the step due to the film thickness of the light-shielding layer to 0.4 μm or less is prepared. It was confirmed that it was possible.

It is typical sectional drawing about an example of a liquid crystal panel. It is typical sectional drawing about another example of a liquid crystal panel. It is typical sectional drawing explaining the level | step difference of the pixel part of a color filter. It is a typical longitudinal section showing an example of a color filter concerning the present invention. It is a figure which shows the reflectance of visible light of the titanium oxynitride (sample A) obtained by manufacture example 1. FIG. It is a figure which shows the reflectance of visible light of the titanium oxynitride (sample B) obtained by manufacture example 2. FIG. It is a figure which shows the reflectance of visible light of the titanium oxynitride (sample C) obtained by manufacture example 3. FIG. It is a figure which shows the reflectance of visible light of the titanium oxynitride (sample D) obtained by manufacture example 4. FIG. It is a figure which shows the reflectance of visible light of the titanium oxynitride (sample E) obtained by the comparative manufacture example 1. FIG. It is a figure which shows the reflectance of visible light of commercially available titanium black (the Mitsubishi Materials make, 13M-C). It is a figure which shows the reflectance of visible light of Example 11, Example 14, and Example 15. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Color filter 2 ... Electrode board 3 ... Gap part 4 ... Sealing material 5 ... Transparent substrate 6 ... Black matrix layer 7 (7R, 7G, 7B) ... Colored layer 8 ... Protective film 9 ... Transparent electrode film 10 ... Orientation film 11 ... Pearl 12 ... Columnar spacer 20 ... Pixel surface 21 ... Vertex of the part on which the pixel has climbed 22 ... Step 101,102 ... Color liquid crystal display device 103 ... Color filter

Claims (11)

Composition formula: TiNxOy · nSiO ₂ (in the composition formula, Ti represents a titanium atom, N represents a nitrogen atom, O represents an oxygen atom, Si represents a silicon atom, x represents a ratio of a nitrogen atom to a titanium atom, and y represents a titanium atom) Represents the ratio of oxygen atoms, x and y can each be a real number greater than 0 and less than 2. n represents the molar ratio of SiO _{2 to} TiNxOy, and n represents a real number in the range of 0 ≦ n ≦ 0.05. The nitrogen atom represented by N is contained in the range of 17 wt% or more and less than 23 wt%, the specific surface area is in the range of 5 to 30 m ² / g, and an X-ray diffractometer is used. A black resin composition for display elements, comprising at least a titanium oxynitride having a measured crystallite diameter in the range of 17 to 25 nm and a curable binder system.   The titanium oxynitride has a reflectance at a wavelength of 650 nm measured using an ultraviolet-visible spectrophotometer of at least 11%, and a minimum value of the reflectance in a wavelength range of 400 to 800 nm is 11.5% or less. The black resin composition for display elements according to claim 1, wherein The titanium oxynitride, TiNxOy · nSiO ₂ comprise a range of 19 to 22 wt% nitrogen atom represented by N, claim 1 or 2 display device for black resin composition according to.   The black resin composition for display elements according to any one of claims 1 to 3, wherein a ratio y / x of y to x represented by TiNxOy of the titanium oxynitride is in a range of 0.10 to 0.60. .   The display according to any one of claims 1 to 4, wherein the titanium oxynitride particle surface is coated with an inorganic compound and / or an organic compound in a range of 0.01 to 30% by weight with respect to titanium oxynitride. Black resin composition for device.   The black resin composition for display elements according to claim 1, wherein the curable binder system is photosensitive. The black resin composition for display elements in any one of Claims 1 thru | or 6 containing the compound represented by following formula (1) in the said curable binder system.

(Wherein R ^{1 to} R ¹⁴ are each independently any one of hydrogen, hydroxyl group, amino group, carboxyl group, halogen, ketone group, aromatic group, or aliphatic group, provided that said aromatic group The group and the aliphatic group may include a structure selected from a branched structure and an alicyclic structure, and are selected from an ether bond, an ester bond, an amino bond, an amide bond, a thioether bond, and an unsaturated bond in the middle of the group. One or more kinds may be contained, and one or more kinds selected from a hydroxyl group, an amino group, a carboxyl group, a halogen, a carbonyl group, and an aromatic group may be contained at the terminal of the group.   Furthermore, the black resin composition for display elements in any one of Claims 1 thru | or 7 which contains 3-20 weight% of carbon black with respect to the whole pigment containing the said titanium oxynitride.   The indication in any one of Claims 1 thru | or 8 whose weight ratio (P / V) of the pigment (P) containing the said titanium oxynitride and solid content (V) other than a pigment is 0.5-3.0. Black resin composition for device.   The black resin composition for display elements according to any one of claims 1 to 9, which is used for a color filter.   The member for display elements provided with the light shielding layer formed using the black resin composition in any one of the said Claims 1 thru | or 10.

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