JP6119104B2 - Photosensitive black resin composition, resin black matrix substrate and touch panel using the same - Google Patents

Description

  The present invention relates to a photosensitive black resin composition, a resin black matrix substrate using the same, and a touch panel.

  A color filter is usually manufactured by a method in which different hues of red, green, and blue are sequentially formed in a striped or mosaic color pattern on the surface of a transparent substrate such as glass or plastic sheet on which a black matrix is formed. Yes. The black matrix used as the light-shielding film plays a role of preventing a decrease in contrast and color purity due to light leakage between pixels.

  On the other hand, a black matrix is similarly formed as a light-shielding film on a touch panel substrate. However, since it is directly visible through glass, it is required to adjust the reflection color of the coating film to a desired characteristic. Specifically, it is necessary to match the color tone of the black matrix of the touch panel and the housing, and it is required to adjust the reflection color tone of the black matrix from an achromatic color to a blue color tone. The black matrix of the touch panel substrate is formed on a cover glass or a cover film facing the sensor substrate, and is generally formed of printing ink. Printing ink is generally made by mixing carbon black with non-photosensitive resin, and since the ratio of carbon black in the resin is low, it is possible to easily adjust the chromaticity of the light-shielding film and to have high insulation properties. However, the light shielding property per unit film thickness is very low (OD = 0.4 to 0.5 / μm). On the other hand, there is an increasing demand for weight reduction and visibility improvement of a touch panel, and technical development is progressing to simultaneously form a light shielding film and a touch sensor on a cover glass (Patent Document 1). In such a case, an electrode or the like is formed after forming a black matrix on the cover glass. However, when printing ink is used, it is 10 μm or more in order to obtain a desired light shielding property (OD = 4.0). Therefore, there is a problem that the transparent electrode is disconnected at a step at the boundary with the opening of the black matrix. Therefore, a black material for black matrix having high light shielding properties in addition to high insulation properties is required.

  By using titanium oxynitride or titanium nitride as a light-shielding material, it becomes possible to easily form a resin black matrix having a sufficiently high resistance value and high light-shielding property, but its reflection color exhibits a strong redness, There was a problem in visibility. On the other hand, a technique of adding carbon black to titanium oxynitride (Patent Document 2) and a technique of using titanium nitride with a small particle diameter as a light shielding material (Patent Document 3) are disclosed in order to improve the reflection color. However, all of them are insufficient for applications such as a touch panel where the demand for reflection chromaticity is strict, and further improvement to an achromatic and bluish tone is necessary.

  In addition, studies have been made to solve various problems by using a mixture of carbon black and organic pigment as a light shielding material. Specifically, yellow, blue, purple, yellow, red, blue A light-shielding film (Patent Document 4) using a resin composition in which pigments are mixed and pseudo-blackened, and a resin composition in which transmittance at a specific wavelength is controlled by using a mixture of a blue pigment and a yellow pigment. A light-shielding film (Patent Document 5), a black photosensitive resin composition that can be sufficiently photocured even in a thick film by mixing a red pigment, a yellow pigment, and a leuco dye to be blackened (Patent Document 6), etc. Is mentioned. However, since the light shielding property per unit film thickness is low in any case, it is necessary to increase the film thickness in order to obtain a desired light shielding property. Also, the reflection color tone has not been studied.

JP 2009-301767 A JP 2008-260927 A JP 2009-58946 A Japanese Patent Laid-Open No. 10-288703 JP 2012-22267 A Japanese Patent No. 4752650

  The present invention was devised in view of the drawbacks of the prior art, and the object of the present invention is a resin having a blue reflection color characteristic and an excellent visibility while having a high light-shielding property and a high insulating property. A photosensitive black resin composition capable of easily forming a black matrix is provided. By using such a photosensitive black resin composition, a resin black matrix having excellent visibility and sufficient light-shielding properties can be formed as a thin film.

  As a result of intensive studies to solve the problems of the prior art, the present inventors can solve the problems of the present invention by using a mixture of carbon black and a specific non-black pigment as a light shielding material as follows. I found.

That is, the object of the present invention is achieved by the following configuration.
(1) As at least a light shielding material, it contains (A) a black pigment, and (B) a non-black pigment, (C) an alkali-soluble resin, (D) a reactive monomer, (E) a radical photopolymerization initiator, and ( F) A photosensitive black resin composition containing an organic solvent, the weight ratio of (A) black pigment being 60% by weight or more and 95% by weight or less based on the total weight of the light shielding material, and (A) as a black pigment And (A-1) carbon black, (B) a non-black pigment, (B-1) a yellow pigment, and (B-2) a red pigment, and a film thickness of 1 on a non-alkali glass having a thickness of 0.7 mm. chromaticity values to form a resin black matrix of .0μm the reflective chromaticity was measured from alkali-free glass surface (a *, b *) is characterized in that Do with a * ≦ 0.2 and b * ≦ 0 A photosensitive black resin composition.
(2) The photosensitive black resin composition according to (1), wherein the weight ratio of the (B-1) yellow pigment to the total weight of the (B) non-black pigment is 30% by weight or more and 70% by weight or less.
(3) The photosensitive black resin composition according to (1) or (2), wherein the (B-1) yellow pigment is a yellow pigment selected from at least PY129, PY138, PY139, PY150, and PY185.
(4) The photosensitive black resin composition according to any one of (1) to (3), wherein the (B-2) red pigment is a red pigment selected from at least PR177, PR179, and PR254.
(5) The photosensitive black resin composition according to any one of (1) to (4), wherein (A-1) carbon black is surface-modified with an organic group comprising a non-polymer group. object.
(6) The photosensitivity according to any one of (1) to (5), which contains (A-2) titanium nitride in addition to (A-1) carbon black as the (A) black pigment. Black resin composition.
(7) The photosensitive black resin composition according to any one of (1) to (6), wherein the weight ratio of the carbon black (A-1) is 50% by weight or more based on the total weight of the (A) black pigment. object.
(8) The photosensitive black resin composition according to any one of (1) to (7), which is for a touch panel.
(9) A resin black matrix obtained by applying the black resin composition according to any one of (1) to (8) on a transparent substrate and forming a pattern is formed. Resin black matrix substrate.
(10) A touch panel comprising the resin black matrix substrate according to (9).

  By using the black resin composition of the present invention, a resin black matrix having high light shielding properties and excellent reflective color characteristics can be easily obtained. Furthermore, it becomes possible to form a resin black matrix having excellent insulating properties in a thin film, and a black matrix substrate for a touch panel having excellent reliability can be obtained.

Hereinafter, the present invention will be described in more detail.
The photosensitive black resin composition of the present invention contains (A) a black pigment and (B) a non-black pigment as a light shielding material, (C) an alkali-soluble resin, (D) a polyfunctional acrylic monomer, (E) light. It consists of a radical polymerization initiator and (F) an organic solvent. In particular, (A) a black pigment and (B) a non-black pigment are contained as a light-shielding material, at least (A) a black pigment as (A-1) carbon black, and (B) a non-black pigment as (B-1 It is important to use a yellow pigment and (B-2) a red pigment, and desirable characteristics are shown below.

  The black resin composition of the present invention includes printing ink, inkjet ink, photomask preparation material, printing proof preparation material, etching resist, solder resist, plasma display panel (PDP) partition, dielectric pattern, electrode (conductor circuit) ) It can be used for the production of light-shielded images such as patterns, wiring patterns of electronic components, conductive pastes, conductive films, and black matrices. Preferably, in order to improve the display characteristics of a color filter used in a color liquid crystal display device or the like, a light-shielded image (including a black matrix) is provided on the interval portion of the coloring pattern, the peripheral portion, and the outside light side of the TFT. It can be suitably used for a light shielding film for a touch panel.

  Particularly preferably, a liquid crystal display device, a plasma display device, an EL display device equipped with an inorganic EL, a CRT display device, a black edge provided at the periphery of a display device equipped with a touch panel, red, blue, green It is suitably used as a black matrix such as a grid-like or stripe-like black portion between colored pixels, a dot-like or linear black pattern for shielding a TFT. In particular, since it has excellent reflection color characteristics, light shielding properties, and insulation properties, it is particularly suitably used as a black matrix for touch panels.

  The black resin composition of the present invention contains (A) a black pigment and (B) a non-black pigment as a light shielding material, and at least (A) a black pigment as (A-1) carbon black, (B) non It is important to use (B-1) a yellow pigment and (B-2) a red pigment as the black pigment. Further, (A) the weight ratio of the black pigment to the total weight of the light shielding material is from 60% by weight to 95%. It is necessary to make the weight percent or less. By setting the composition of the light shielding material as described above, a black resin composition having a high light shielding property and capable of forming a black matrix having a bluish reflective color characteristic can be obtained. Here, the bluish reflection color characteristic specifically refers to the reflection spectrum for the standard light source D65 when the reflection chromaticity of the black matrix formed on the transparent substrate is measured from the surface of the transparent substrate. In the chromaticity values (a *, b *) calculated by the CIE L * a * b * color system, a * ≦ 0.5 and b * ≦ 0.

  As the (A) black pigment in the present invention, it is important to use at least (A-1) carbon black. By using carbon black, the reflection chromaticity of the coating film can be easily achromatic. It becomes.

On the other hand, from the viewpoint of improving the light shielding property and the insulating property, other black pigments may be used in combination, and can be used without particular limitation from black organic pigments, inorganic pigments and the like. As black organic pigments, perylene black, aniline black, etc., as inorganic pigments, graphite and fine metal particles such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, metal oxides, Complex oxides, metal sulfides, metal nitrides, metal carbides and the like can be mentioned, and (A-2) titanium nitride or titanium carbide is more preferably used because it has both high light shielding properties and high insulating properties. Among these, as described later, it is more preferable to use titanium nitride. Here, the titanium nitride includes titanium nitride as a main component, and is usually a low-order titanium oxide and TiN _x O that can be expressed as titanium oxide TiO ₂ , Ti _n O _2n-1 (1 ≦ n ≦ 20) as subcomponents. A material containing titanium oxynitride which can be represented by _y (0 <x <2.0, 0.1 <y <2.0). These black pigments may be used alone or in combination of two or more in addition to carbon black.

  It is important to use (B-1) a yellow pigment and (B-2) a red pigment as the (B) non-black pigment in the present invention. It is possible to suppress the chromaticity from becoming yellow and adjust it to blue, and it is possible to form a coating film with better visibility.

Examples of the (B-1) yellow pigment in the present invention can be used without particular limitation. Specifically, pigment yellow (hereinafter abbreviated as PY) PY12, PY13, PY17, PY20, PY24, PY83, PY86. , PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY138, PY139, PY147, PY148, PY150, PY153, PY154, PY166, PY168, PY185, and the like. It is more preferable to use PY129, PY138, PY139, PY150, and PY185 from the viewpoints of coloring power, heat resistance, and light resistance. The (B-2) red pigment in the present invention can be used without any particular limitation. Specifically, Pigment Red (hereinafter abbreviated as PR) 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR180, PR190, PR192, PR209, PR215, PR216, PR217, PR220, PR223, PR224, PR226, PR227, PR228, PR240, PR242 and the like can be mentioned. From the viewpoint of coloring power, heat resistance, and light resistance, it is more preferable to use PR177, PR179, and PR254. On the other hand, other non-black pigments may be used in combination for the purpose of finer chromaticity adjustment. The inorganic pigment can be used without any particular limitation. Organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, or metal-free phthalocyanine, aminoanthraquinone, diaminodianthraquinone, anthra Anthraquinone pigments such as pyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindoline pigment, isoindolinone pigment Examples thereof include pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

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

  As (A-1) carbon black in this invention, it is preferable to use carbon black which improved insulation by surface-treating. The treatment for enhancing the insulation is generally performed by surface coating with a resin (Japanese Patent Laid-Open No. 2002-249678), wet oxidation treatment on a surface (Japanese Patent No. 4464081), and organic groups composed of non-polymer groups. Surface modification (Japanese translations of PCT publication No. 2008-517330) etc. are known.

  More preferably, it is preferable to use a carbon black surface-modified with an organic group consisting of a non-polymer group, and in particular, by using a carbon black surface-modified with an organic compound having a sulfonic acid group, high insulation and high temperature treatment Since the fall of the insulation in can be suppressed, it is more preferable.

  In order to make the effect in the present invention more remarkable, it is preferable to use carbon black having a specific surface composition. Specifically, the surface composition of carbon black has a carbon atom ratio of 95% or less, and sulfur. The atomic ratio is preferably 0.5% or more, more preferably the carbon atomic ratio is 95% or less, and the sulfur atomic ratio is preferably 1.0% or more, more preferably the carbon atomic ratio is 90%. % And the sulfur atom ratio is 1.0% or more. The higher the proportion of sulfur atoms in the carbon black surface, the more effectively the binder resin is adsorbed to the carbon black, thereby making it possible to suppress contact between the carbon blacks due to steric hindrance and improving the insulation of the resin black matrix. To do.

  The sulfur atom component present on the surface of carbon black is present in the form of disulfide, carbon disulfide, and oxide, but is present in the state of oxide to make the effect of the present invention remarkable. Specifically, it is desirable to exist in the state of SO and SOx (2 ≦ x ≦ 4). The state of S atoms on the surface of carbon black can be confirmed by X-ray photoelectron spectroscopy (XPS), and the S2p peak component is a component attributed to C—S and S—S, and SO and SOx (2 ≦ x ≦ The abundance ratio can also be confirmed by dividing into the components belonging to 4). In the carbon black in the present invention, the ratio of sulfur atom components present on the surface to components derived from SO and SOx is preferably 70% or more, and more preferably 80% or more. The higher the proportion of sulfur atom components present on the surface that are components derived from SO and SOx, the higher the insulating properties, and the lower the insulating properties during high-temperature treatment, which is preferable. The mechanism by which higher insulation and thermal stability are obtained due to the large amount of components derived from SO and SOx is unknown, but it is presumed that the adsorption of the binder resin to carbon black becomes stronger. The

The specific surface area of the carbon black used in the present invention is not particularly limited, value measured by the BET method of nitrogen adsorption, it is preferable that there below ^{10 m} 2 / g or more 600 meters ² / g, still more 20 m ² / G or more and 200 m ² / g or less, more preferably 20 m ² / g or more and 100 m ² / g or less. When the specific surface area is large, that is, when the primary particle size is small, the particles are likely to aggregate, so that it becomes difficult to stabilize the dispersion and storage stability is deteriorated. On the other hand, when the specific surface area is small, that is, when the primary particle diameter is large, the light shielding property is lowered, or the carbon blacks are in contact with each other in the resin coating film.

  In order to make the effect of the present invention remarkable, it is preferable to use (A-2) titanium nitride in addition to (A-1) carbon black as (A) black pigment, and desirable characteristics of the titanium nitride Is described in detail below, but is not limited thereto.

  As (A-2) titanium nitride used in the present invention, the diffraction angle 2θ of the peak derived from the (200) plane when the CuKα ray is used as an X-ray source is 42.5 ° or more and 43.2. It is preferably not more than °, more preferably not less than 42.5 ° and not more than 42.8 °, and more preferably not less than 42.5 ° and not more than 42.7 °. By using titanium nitride particles having a diffraction angle θ in this range as a light shielding material, it becomes possible to achieve high light shielding properties while keeping the concentration of the light shielding material in the black resin composition low. Since it has a transmittance, it is possible to easily form a resin black matrix having a high definition and a good taper shape.

The X-ray diffraction spectrum of the titanium compound shows that when CuKα ray is used as the X-ray source, TiN has a peak derived from the (200) plane as the strongest peak, and 2θ = 42.5 ° in the vicinity of TiO and (200) plane of TiO The peak derived from is seen in the vicinity of 2θ = 43.4 °. On the other hand, although not the strongest peak, the peak derived from the (200) plane of anatase TiO ₂ is in the vicinity of 2θ = 48.1 °, and the peak derived from the (200) plane of rutile TiO ₂ is 2θ = 39. Observed around 2 °. Therefore, a titanium compound having a crystal structure having nitrogen atoms and oxygen atoms has the strongest peak in the diffraction angle 2θ range of 42.5 ° to 43.4 °, and is in a crystalline state containing a large amount of oxygen atoms. The more the peak position is shifted to the higher angle side with respect to 42.5 °. In titanium oxynitride obtained by nitriding titanium oxide and insufficiently reduced by nitriding, the strongest peak is confirmed at a diffraction angle 2θ of 42.9 ° to 43.2 ° (Japanese Patent Laid-Open No. 2006-209102). Publication). When titanium oxide TiO ₂ is contained as an accessory component, the peak derived from anatase TiO ₂ (101) as the strongest peak is in the vicinity of 2θ = 25.3 ° and derived from rutile TiO ₂ (110). A peak is observed in the vicinity of 2θ = 27.4 °. However, since TiO ₂ is white and causes a reduction in the light shielding properties of the black matrix, it is preferably reduced to such an extent that it is not observed as a peak.

  The crystallite size constituting the (A-2) titanium nitride particles can be determined from the half-value width of the X-ray diffraction peak, and is calculated using the Scherrer equation shown in the following equations (1) and (2).

Here, K = 0.9, λ (0.15418 nm), β _e : half width of diffraction peak, β _o : correction value of half width (0.12 °). Where β, β _e and β _o are calculated in radians.

  The crystallite size is preferably 10 nm or more, further preferably 10 nm or more and 50 nm or less, and more preferably 10 or more and 30 nm or less. When titanium nitride particles having a crystallite size of less than 10 nm are used, there arises a problem that the light blocking property of the black matrix is lowered and further the dispersibility is deteriorated. On the other hand, when the thickness exceeds 50 nm, the light shielding property is lowered, and further, sedimentation is likely to occur, and the storage stability is deteriorated. However, the smaller the crystallite size, the lower the light-shielding property, but the reflection color approaches an achromatic color. Therefore, in the present invention, a reasonably small one is preferable.

The specific surface area of (A-2) titanium nitride particles in the present invention can be determined by the BET method, and the value is preferably 5 m ² / g or more and 100 m ² / g or less, more preferably 10 m ² / g or more and 100 m ^2. / g or less, and more preferably not more than ^{30 m} 2 / g or more 100 m ² / g. Further, from the specific surface area obtained by the BET method, the particle diameter when the particles are assumed to be perfect spheres and the particle diameter is uniform can be obtained by the following equation (3).

  BET conversion average particle diameter (nm) = 6 / (S × d × 1000) (3).

Here, S: specific surface area (m ² / g), d: density (g / cm ³ ), d = 5.24 (g / cm ³ ) for titanium nitride, d = 4 for titanium oxynitride 3 (g / cm ³ ).

  When the specific surface area is small, that is, when the primary particle size is large, it is difficult to finely disperse the particles, the particles settle during storage, the flatness of the resin black matrix decreases, or the glass adheres closely. There arises a problem that the performance is lowered. On the other hand, when the specific surface area is large, that is, when the primary particle size is small, the particles are likely to re-aggregate during dispersion, so that the dispersion stability tends to deteriorate, or when the resin black matrix is used, there is sufficient concealment as a light shielding material. This is not preferable because the OD value is lowered without being obtained.

  Moreover, although it can be said that the primary particle of the particle is a collection of several crystallites, it is preferably composed of a single crystallite. That is, the relationship between the crystallite size obtained from the half width of the X-ray diffraction peak and the particle diameter obtained from the specific surface area is preferably in the range of the following formula (4).

BET equivalent average particle diameter (nm) <crystallite size (nm) × 2 (4)
(A-2) Titanium nitride particles used in the present invention contain TiN as a main component, and are usually noticeable when oxygen is mixed during the synthesis, particularly when the particle diameter is small. Therefore, some oxygen atoms are contained. A smaller amount of oxygen is preferable because a higher OD value can be obtained, and it is particularly preferable not to contain TiO ₂ as a subcomponent. However, the smaller the oxygen content, the red the color of the reflection, and therefore it is preferable that oxygen atoms are appropriately contained. The oxygen atom content is 5 wt% or more and 20 wt% or less, and more preferably 8 wt% or more and 20 wt% or less.

  Titanium atom content is analyzed by ICP emission spectroscopy, nitrogen atom content is analyzed by inert gas melting-thermal conductivity method, and oxygen atom content is analyzed by inert gas melting-infrared absorption method. can do.

  The ratio of the (A) black pigment to make the total weight of the light shielding material needs to be 60% by weight to 95% by weight, and more preferably 70% by weight to 90% by weight. When the proportion of the black pigment is small, the reflection color is preferable because it exhibits a more bluish achromatic color. However, since the light-shielding performance per unit film thickness is reduced, the film thickness of the light-shielding film is required to obtain a desired light-shielding property. When the transparent electrode is formed on the light shielding film, problems such as disconnection occur. On the other hand, if the proportion of the black pigment is large, the reflection color cannot be set to a desired color tone.

  In order to make the effect in the present invention remarkable, the weight ratio of (B-1) yellow pigment to the total weight of (B) non-black pigment is preferably 25% by weight or more and 75% by weight or less. 30% by weight or more is preferable, and 50% by weight or more is more preferable. Moreover, it is more preferable to set it as 70% or less. When the proportion of the yellow pigment is small, the reflection chromaticity b * of the light-shielding film increases, and the bluish color becomes weak. On the other hand, when the proportion of the yellow pigment is large, the reflection chromaticity a * of the light-shielding film is increased, and yellowing is not preferable.

  The weight ratio of (A-1) carbon black to the total weight of the (A) black pigment is preferably 25% by weight or more, and more preferably 50% by weight or more. If the proportion of carbon black is small, the reflection chromaticity of the coating film is not achromatic, which is not preferable.

  In the present invention, (C) an alkali-soluble resin is an essential component, but it acts as a binder for the pigment and is soluble in an alkali developer in the development process when forming a pattern such as a black matrix. If it is, it will not specifically limit. Among these, an alkali-soluble resin having a carboxyl group is preferable, and a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound can be preferably used. Examples of the unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid, dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid, or acid anhydrides thereof, phthalic acid mono (2 -(Meth) acryloyloxyethyl) and other polycarboxylic acid monoesters. In particular, an acrylic polymer containing a structural unit derived from (meth) acrylic acid is preferable, and a carboxylic acid contained in the structural unit is reacted with a compound containing an ethylenically unsaturated group and an epoxy group. When the obtained acrylic polymer is used, the sensitivity during exposure and development is improved, so that it can be preferably used. As an ethylenically unsaturated group, an acryl group and a methacryl group are preferable.

  These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, methacryl Isopropyl acrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate N-pentyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate and other unsaturated carboxylic acid alkyl esters, styrene, p-methyls Rene, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene, α-methylstyrene, (crosslinked) cyclic hydrocarbon groups such as tricyclodecanyl (meth) acrylate, and unsaturated carboxylic acids such as aminoethyl acrylate Acid aminoalkyl esters, unsaturated glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile, 1 Aliphatic conjugated dienes such as 1,3-butadiene and isoprene, polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate having acryloyl group or methacryloyl group at each end. Rate, and poly butyl methacrylate, but is not limited thereto. In particular, an acrylic polymer comprising (meth) acrylic acid and benzyl (meth) acrylate is particularly preferable from the viewpoints of dispersion stability and pattern processability.

  When the acrylic polymer is added in an amount of 5 to 50%, preferably 7 to 40%, based on the pigment at the time of pigment dispersion, a pigment dispersion having a highly stable dispersion can be obtained.

  In addition to the acrylic polymer obtained by reacting (meth) acrylic acid contained in the structural unit described above with a compound containing an ethylenically unsaturated group and an epoxy group, the side chain is ethylenic. An acrylic polymer having an unsaturated group can be preferably used. Specific examples include a copolymer described in Japanese Patent No. 3120476, JP-A-8-262221, or a photocurable resin “Cyclomer (registered trademark) P” (Daicel), which is a commercially available acrylic polymer. Chemical Industry Co., Ltd.), alkali-soluble cardo resin and the like.

  The average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 to 40,000 (measured by gel permeation chromatography using tetrahydrofuran as a carrier and converted using a standard polystyrene calibration curve). Furthermore, a polymer having an average molecular weight of 8,000 to 30,000 and an acid value of 70 to 150 (mg KOH / g) is from the viewpoints of photosensitive properties, solubility in ester solvents, solubility in alkaline developers, and residue control. Most preferred.

  (D) As the reactive monomer, a polyfunctional or monofunctional acrylic monomer or oligomer can be used. Examples of the polyfunctional monomer include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylate, anhydrous Phthalic acid propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) acrylate, Japanese Patent No. 3621533 and Japanese Patent Application Laid-Open No. 8-278630 Or full propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol Nord A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate and its acid-modified product, dipentaerythritol hexa ( (Meth) acrylate and its acid-modified product, dipentaerythritol penta (meth) acrylate and its acid-modified product, 2,2-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] propane, bis [4- ( 3-acryloxy-2-hydroxypropoxy) phenyl] methane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] sulfone, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl Ether, 4,4′-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] cyclohexane, 9,9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9 -Bis [3-methyl-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-chloro-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, bis Examples thereof include phenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, biscresol full orange acrylate, and biscresol full orange methacrylate. These can be used alone or in combination.

  By selecting and combining these polyfunctional monomers and oligomers, it is possible to control the sensitivity and processability characteristics of the resist. In particular, in order to increase sensitivity, it is desirable to use a compound having a functional group of 3 or more, more preferably 5 or more. In particular, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and acid-modified products thereof are used. preferable. In addition, an unsaturated group-containing alkali-soluble monomer obtained by reacting a polybasic carboxylic acid or its acid anhydride with a reaction product of an epoxy compound having two glycidyl ether groups and methacrylic acid is also developable and processed. It is preferably used from the viewpoint of sex. Further, the combined use of (meth) acrylate having a fluorene ring having a large amount of aromatic rings and high water repellency in the molecule is preferable because the pattern can be controlled to a desired shape during development.

  (E) Although there is no restriction | limiting in particular as radical photopolymerization initiator, It is preferable to contain an alkylphenone series and / or oxime ester series photopolymerization initiator.

  Examples of the alkylphenone-based photopolymerization initiator include α-aminoalkylphenone and α-hydroxyalkylphenone, and α-aminoalkylphenone is particularly preferable from the viewpoint of high sensitivity. For example, 2-benzyl which is 2,2-diethoxyacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, BASF Corporation “Irgacure®” 369 2-Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl], which is BASF Corp. “Irgacure®” 379 Examples include -1- [4- (4-morpholinyl) phenyl] -1-butanone, 1-hydroxycyclohexyl phenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one.

  As a specific example of an oxime ester photopolymerization initiator, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime), which is BASF Corporation “Irgacure (registered trademark)” OXE01 ] Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyl) which is BASF Corporation "Irgacure (registered trademark)" OXE02 Oxime), “Adeka (registered trademark) Optomer” N-1818, N-1919, “Adeka Cruz” NCI-831 manufactured by Asahi Denka Kogyo Co., Ltd., and the like.

  In addition to these photopolymerization initiators, inorganic compounds such as benzophenone compounds, oxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, carbazole compounds, triazine compounds, phosphorus compounds or titanates A known photopolymerization initiator such as a photopolymerization initiator can also be used in combination. For example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, Thioxanthone, 2-chlorothioxanthone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthate Laquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mer Hept benzothiazole, 2-mercaptobenzoxazole, 4-(p-methoxyphenyl) -2,6-- such as (trichloromethyl) -s-triazine and the like.

  The organic solvent (F) used in the black resin composition of the present invention is not particularly limited, and esters, aliphatic alcohols, ketones and the like can be used.

  Specific esters include benzyl acetate (boiling point 214 ° C.), ethyl benzoate (boiling point 213 ° C.), γ-butyrolactone (boiling point 204 ° C.), methyl benzoate (boiling point 200 ° C.), diethyl malonate (boiling point 199 ° C.), 2-ethylhexyl acetate (bp 199 ° C.), 2-butoxyethyl acetate (bp 192 ° C.), 3-methoxy-3-methyl-butyl acetate (bp 188 ° C.), diethyl oxalate (bp 185 ° C.), ethyl acetoacetate ( Boiling point 181 ° C.), cyclohexyl acetate (bp 174 ° C.), 3-methoxy-butyl acetate (bp 173 ° C.), methyl acetoacetate (bp 172 ° C.), ethyl-3-ethoxypropionate (boiling point 170 ° C.), 2- Ethyl butyl acetate (boiling point 162 ° C), isopentyl propio (Boiling point 160 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), pentyl acetate (boiling point 150 ° C), propylene glycol monomethyl ether acetate (boiling point 146 ° C) ) And the like, but is not limited thereto.

  Among these solvents, acetic acid ester type or propionic acid ester type solvents include 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, 3-methoxy-butyl. Particularly preferred are acetate and propylene glycol monomethyl ether acetate.

  In addition to the above solvents, propylene glycol monomethyl ether (boiling point 120 ° C.), propylene glycol monoethyl ether (boiling point 133 ° C.), propylene glycol tertiary butyl ether (boiling point 153 ° C.), dipropylene glycol monomethyl ether (boiling point 188 ° C.) Aliphatic ethers such as propylene glycol derivatives such as, aliphatic esters other than those described above, for example, ethyl acetate (boiling point 77 ° C.), butyl acetate (boiling point 126 ° C.), isopentyl acetate (boiling point 142 ° C.), or butanol ( Boiling point 118 ° C.), aliphatic alcohols such as 3-methyl-2-butanol (boiling point 112 ° C.), 3-methyl-3-methoxybutanol (boiling point 174 ° C.), ketones such as cyclopentanone and cyclohexanone, xylene ( Boiling point 14 ° C.), ethylbenzene (boiling point 136 ° C.), solvent naphtha (petroleum fraction: it is also possible to use a solvent such as boiling point 165 to 178 ° C.).

  Furthermore, since application by a die coating apparatus has become mainstream with an increase in the size of the substrate, it is preferable to use a mixed solvent of two or more components in order to achieve appropriate volatility and drying properties. When the boiling points of all the solvents constituting the mixed solvent are 150 ° C. or less, the film thickness uniformity cannot be obtained, the film thickness of the coating end part is increased, the pigment is applied to the base part for discharging the coating liquid from the slit. Aggregates are formed, causing many problems that streaks occur in the coating film. On the other hand, when the mixed solvent contains a large amount of solvent having a boiling point of 200 ° C. or higher, the surface of the coating film becomes sticky and sticking occurs. Accordingly, a mixed solvent containing 30 to 75% by mass of a solvent having a boiling point of 150 ° C. or higher and 200 ° C. is desirable.

  In the photosensitive black resin composition of the present invention, it is preferable to add an adhesion improver for the purpose of improving the adhesion to the base substrate, and specifically, a silane coupling agent can be suitably used. The silane coupling agent is not particularly limited, and examples thereof include, but are not limited to, a silane coupling agent having a functional group such as a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, or an amino group. is not. Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- ( 2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3 -A Nopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, p-trityltrimethoxysilane and the like are preferable.

  As addition amount, 1-15 mass% is preferable with respect to the total amount of the solid component of the photosensitive black resin composition, ie, the total of a light shielding material, alkali-soluble resin, and a reactive monomer, and 2-10 mass% is more preferable. If the amount is less than 1% by mass, the effect of improving the adhesiveness is not sufficient. If the amount is more than 15% by mass, a fine pattern is lost in alkali development and the resolution is lowered.

  In the photosensitive black resin composition of the present invention, it is preferable to add a pigment dispersant in order to disperse the light shielding material uniformly and stably in the resin solution. Examples of pigment dispersants include polyester polymer pigment dispersants, acrylic polymer pigment dispersants, polyurethane polymer pigment dispersants, polyallylamine polymer dispersants, pigment derivatives, cationic surfactants, and nonionic interfaces. Examples thereof include an activator, an anionic surfactant, and a carbodiimide pigment dispersant.

  Various kinds of dispersants including a dispersant having only an amine value, a dispersant having only an acid value, a dispersant having an amine value and an acid value, and a dispersant having neither an amine value nor an acid value However, in order to make the effect of the present invention remarkable, it is more preferable to use a dispersant having an amine value, and it is more preferable to use a dispersant having only an amine value. By using a dispersant having an amine value, it is possible to more stably finely disperse the carbon black of the present invention surface-modified with a sulfonic acid group, and to form a coating film having high insulating properties. Become.

  Specific examples of the polymer dispersant having only an amine value include Dispersic 102, Dispersic 160, Dispersic 161, Dispersic 162, Dispersic 2163, Dispersic 2164, Dispersic 166, Dispersic 167, and Dispersic 168. , Dispersic 2000, Dispersic 2050, Dispersic 2150, Dispersic 2155, Dispersic LPN6919, Dispersic LPN21116, Dispersic LPN 21234, Dispersic 9075, Dispersic 9077 (above, manufactured by BYK Chemie); EFKA 4015, EFKA 4020, EFKA 4046, EFKA 4047, EFKA 4050, EFKA 4055 EFKA 4060, EFKA 4080, EFKA 4300, EFKA 4330, EFKA 4340, EFKA 4400, EFKA 4401, EFKA 4402, EFKA 4403, EFKA 4800 (above, manufactured by BASF); Although it is mentioned, it is not limited to these. Among polymer dispersants having only an amine value, it is more preferable to use a polymer dispersant having at least a tertiary amino group, and specific examples thereof include Dispersic LPN6919, Dispersic LPN21116, and the like.

  Specific examples of the polymer dispersant having an amine value and an acid value include Dispersic 142, Dispersic 145, Dispersic 2001, Dispersic 2010, Dispersic 2020, Dispersic 2025, Dispersic 9076, Anti-Terra-205. (Above, manufactured by Big Chemie); Solsperse 24000 (manufactured by Lubrizol Corp.); Azisper PB821, Azisper PB880, Azisper PB881 (above, Ajinomoto Fine Techno Co., Ltd.) and the like.

  These pigment dispersants are appropriately selected and used according to the type of pigment. These pigment dispersants may be used alone or in combination of two or more. Since these polymer dispersants do not have photosensitivity, there is a concern that the photosensitivity of the target color resist may be deteriorated if added in a large amount. Therefore, an appropriate addition amount considering dispersion stability and photosensitivity is required. Is desirable. Addition of 1 to 50 (mass%), more preferably 3 to 30 (mass%) with respect to the pigment is more preferable because it has the effect of highly stabilizing dispersion without deteriorating the photosensitive performance.

  In addition, a surfactant may be added to the photosensitive black resin composition of the present invention for the purpose of preventing coating properties, smoothness of a colored film, and Benard cell. The addition amount of the surfactant is usually 0.001 to 10% by mass, preferably 0.01 to 1% by mass of the pigment. If the amount added is too small, the coating properties, smoothness of the colored coating and Benard cell are not effective, and if too large, the physical properties of the coating film may be poor. Specific examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, Amphoteric surfactants such as lauryl carboxymethyl hydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, and silicones based on polydimethylsiloxane Surfactants, fluorosurfactants and the like can be mentioned. In the present invention, the surfactant is not limited to these, and one or more surfactants can be used.

  In the photosensitive black composition of the present invention, the weight composition ratio of the light shielding material component / resin component is preferably in the range of 60/40 to 30/70 in order to obtain a black film having a high OD value. Here, the resin component means (C) an alkali-soluble resin, (D) a reactive monomer, and (E) an optical radical polymerization initiator, as well as additives such as an adhesion improver, a surfactant, and a polymer dispersant. Total. If the amount of the resin component is too small, the adhesion of the black coating to the substrate becomes poor. Conversely, if the amount of the light shielding material component is too small, the optical density per unit thickness (OD value / μm) is lowered, causing a problem.

  In the photosensitive black resin composition of the present invention, the solid content concentration of the resin component and the light shielding material component is preferably 2% or more and 30% or less, more preferably 5% or more and 20% from the viewpoint of coating properties and drying properties. The following is preferable.

  In the photosensitive black resin composition of the present invention, a pigment dispersion is prepared by dispersing a pigment directly in a resin solution using a disperser or by dispersing a pigment in water or an organic solvent using a disperser. And then mixed with a resin solution. The method for dispersing the pigment is not particularly limited, and various methods such as a ball mill, a sand grinder, a three-roll mill, and a high speed impact mill can be used, but a bead mill is preferred from the viewpoint of dispersion efficiency and fine dispersion. As the bead mill, a coball mill, a basket mill, a pin mill, a dyno mill, or the like can be used. As the beads of the bead mill, titania beads, zirconia beads, zircon beads and the like are preferably used. The bead diameter used for dispersion is preferably 0.01 mm to 5.0 mm, more preferably 0.03 mm to 1.0 mm. When the primary particle diameter of the pigment and the secondary particles formed by agglomeration of the primary particles are small, it is preferable to use fine dispersed beads of 0.03 mm or more and 0.10 mm or less. In this case, it is preferable to disperse using a bead mill having a centrifugal separator capable of separating fine dispersion beads and dispersion. On the other hand, when dispersing a pigment containing coarse particles of about submicron, it is preferable to use dispersed beads of 0.10 mm or more because sufficient pulverization force can be obtained and the pigment can be finely dispersed.

  The example of the manufacturing method of the resin black matrix board | substrate by the die coating apparatus using the photosensitive black resin composition of this invention is demonstrated. As the substrate, a transparent substrate such as soda glass, non-alkali glass, or quartz glass is usually used, but is not particularly limited thereto. Examples of the die coating apparatus include a single wafer coating apparatus disclosed in Japanese Patent No. 3139358 and Japanese Patent No. 3139359. By this apparatus, the black resin composition (coating liquid) of the present invention is discharged from the die and the substrate is moved, whereby the black resin composition can be applied on the substrate. In this case, since a large number of substrates are applied in a single sheet, when the apparatus is operated for a long time, agglomerates of pigments are formed in the base part for discharging the coating liquid from the slits, which may cause a coating defect and reduce the yield.

  In this case, by providing a step of wiping the base, which is a discharge port of the apparatus, with a solvent containing 40% by mass or more of the ester solvent having a boiling point of 150 ° C. or higher with respect to the total solvent, the coating defect is eliminated and the base is removed. The rate is improved. After applying a black resin composition on a board | substrate by the above, a solvent is removed by air drying, reduced pressure drying, heat drying, etc., and the coating film of a black resin composition is formed. In particular, after providing a vacuum drying step, additional heating and drying in an oven or a hot plate eliminates coating defects caused by convection and improves the yield. The drying under reduced pressure is preferably performed in the range of room temperature to 100 ° C., 5 seconds to 10 minutes, and a degree of vacuum of 500 to 10 (Pa), more preferably a degree of vacuum of 150 to 50 (Pa). Heat drying is preferably performed using an oven, a hot plate or the like at a temperature of 50 to 120 ° C. for 10 seconds to 30 minutes.

  Subsequently, a mask is placed on the coating and irradiated with ultraviolet rays using an exposure apparatus. Next, development is performed with an alkaline developer. It is preferable to use an alkaline developer added with 0.1 to 5% of a surfactant such as a nonionic surfactant because a better pattern can be obtained. Although it does not specifically limit as an alkaline substance used for an alkaline developing solution, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n- Primary amines such as propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH) , Quaternary ammonium salts such as choline, triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol and other alcohol amines, pyrrole, piperidine, 1,8-dia Bicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, organic alkalis such as cyclic amines such as morpholine.

  The concentration of the alkaline substance is 0.01% by mass to 50% by mass. Preferably it is 0.02 mass% to 10 mass%, More preferably, it is 0.02 to 1 mass%. In the case where the developer is an alkaline aqueous solution, a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, N-methyl-2-pyrrolidone may be appropriately added to the developer.

  Among these developers, an aqueous developer of an alkaline aqueous solution is preferable from the viewpoint of working environment and waste developer treatment.

  The development method uses an immersion method, a spray method, a paddle method or the like, but is not particularly limited. After development, a washing process with pure water or the like is added.

The coating film pattern of the obtained black resin composition is then patterned by heat treatment (post-baking). The heat treatment is usually performed in air, in a nitrogen atmosphere, or in a vacuum at 150 to 300 ° C, preferably 180 to 250 ° C, continuously or stepwise for 0.25 to 5 hours. Done.
As described above, the optical density (Optical Density, OD value) of the resin black matrix obtained from the black resin composition of the present invention is 1.5 or more per 1.0 μm film thickness in the visible light range of 380 to 700 nm. And more preferably 2.0 or more. The OD value can be obtained from the following relational expression (5) by measuring using a microspectroscope (MCPD2000 manufactured by Otsuka Electronics).

OD value = log ₁₀ (I ₀ / I) (5)
Here, I _{0 is} incident light intensity, and I is transmitted light intensity.

  The reflection chromaticity of the resin black matrix is measured from the surface of the transparent substrate, and is calculated by the CIE L * a * b * color system using the reflection spectrum for the standard C light source according to the method of JIS-Z8729. The chromaticity values (a *, b *) are preferably a * ≦ 0.2 and b * ≦ 0, more preferably a * ≦ 0.2 and b * ≦ −0.2. Is preferred.

Further, the surface resistance value ρs (Ω / □) of the resin black matrix is preferably 10 ¹⁰ (Ω / □) or more, and more preferably 10 ¹² (Ω / □) or more. The surface resistance value can be obtained by measuring by the method described in “JIS K6911”.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, this invention is not limited to a following example.

<Evaluation method>
[Surface element composition]
The surface element of carbon black was measured by X-ray photoelectron spectroscopy (XPS). ESCALAB220iXL (trade name) was used as the measuring device, monochromatic AlKα1,2 wire (1486.6 eV) was used as the excitation X-ray as measurement conditions, the X-ray diameter was 1 mm, and the photoelectron escape angle was 90 °.

"X-ray diffraction"
X-ray diffraction was measured by a wide-angle X-ray diffraction method (RU-200R manufactured by Rigaku Corporation) with a powder sample packed in an aluminum standard sample holder. As measurement conditions, the X-ray source is CuKα ray, the output is 50 kV / 200 mA, the slit system is 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) is 0.02 °, and the scan speed is It was 2 ° / min. The diffraction angle of the peak derived from the (200) plane observed near the diffraction angle 2θ = 46 ° was measured. Further, from the half width of the peak derived from the (200) plane, the crystallite size constituting the particle was determined using the Scherrer equation of the above-described equations (1) and (2).

[Composition analysis]
The content of titanium atoms was measured by ICP emission spectroscopic analysis (ICP emission spectroscopic analyzer SPS3000 manufactured by Seiko Instruments Inc.). The content of oxygen atoms and nitrogen atoms was measured using (Horiba oxygen / nitrogen analyzer EMGA-620W / C), and the oxygen atoms were converted into inert gas by infrared gas absorption-infrared absorption method. The nitrogen atom was determined by the method.
[Powder volume resistance]
A cylindrical Teflon (registered trademark) sample cell is filled with the sample, electrodes are placed on both ends of the cylinder, a load is applied to the electrode with Shimadzu AUTOGRAPH, and a resistance value is measured with Hioki Low Resistance Meter 3540 Was measured. The volume resistivity ρ was determined from the measured resistance value according to the following formula, and the value at a pressure of 50 kgf / cm ² was taken as the powder volume resistance of the sample.
Powder volume resistance ρ [Ω · cm] = R × S / t (S: sample cross-sectional area, t: sample thickness).

[Specific surface area]
The specific surface area of the particles is the adsorption isotherm at a liquid nitrogen temperature (77 K) of N ₂ gas after vacuum degassing at 100 ° C. using a high precision fully automatic gas adsorption device (“BELSORP” 36) manufactured by Nippon Bell Co., Ltd. The isotherm was analyzed by the BET method to determine the specific surface area. Further, from the value of the specific surface area, the BET equivalent particle diameter was obtained using the above-described formula (3). At this time, d = 5.24 (g / cm ³ ) was used as the specific gravity for titanium nitride particles, and d = 1.80 (g / cm ³ ) was used as the specific gravity for carbon black.

[OD value]
A resin black matrix having a film thickness of 1.0 μm was formed on an alkali-free glass and obtained from the above formula (5) using a microspectroscope (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.).

[Reflection chromaticity]
A resin black matrix having a film thickness of 1.0 μm is formed on an alkali-free glass having a thickness of 0.7 mm, and an ultraviolet / visible / near infrared spectrophotometer (Shimadzu spectrophotometer UV-2500PC) is used. The reflection chromaticity was measured (measurement conditions were a measurement wavelength region; 300 to 780 nm, a sampling pitch: 1.0 nm, a scan speed; a low speed, a slit width; 2.0 nm).

[Surface resistance]
A resin black matrix having a film thickness of 1.0 μm was formed on alkali-free glass, and the surface resistivity (Ω / □) was measured with a high resistivity meter (Hiresta UP, manufactured by Mitsubishi Chemical Corporation).

  The surface resistivity was measured in the same manner after the black matrix was heat-treated in an oven at 250 ° C. for 30 minutes.

Synthesis of acrylic polymer (P-1) Methyl methacrylate / methacrylic acid / styrene copolymer (weight composition ratio 30/40/30) was synthesized by the method described in Example 1 of Japanese Patent No. 3120476, and then glycidyl methacrylate. An acrylic polymer (P-1) powder having characteristics of an average molecular weight (Mw) of 10,000 and an acid value of 110 (mgKOH / g) is obtained by adding 40 parts by weight, reprecipitating with purified water, filtering and drying. Obtained.

Preparation of carbon black dispersion (C-1) The surface element composition of carbon black (CB-Bk1, manufactured by Cabot) whose surface was modified with a sulfonic acid group was C element: 95%, O element: 6%, Na element: 3 %, S element: 2%. Furthermore, the ratio of the component attributed to C—S and S—S and the component attributed to SO and SOx in the S2p peak component is 90:10. The powder volume resistance was 97 Ω · cm, and the BET value was 54 m ² / g.

  175 g of high resistance carbon black (CB-Bk1), 107 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of acrylic polymer (P-1), 94 g of Dispersic LPN-21116 (manufactured by BYK Chemie) as a polymer dispersant Then, 624 g of propylene glycol monoethyl ether acetate was charged into a tank and stirred for 20 minutes with a homomixer (manufactured by PRIMIX) to obtain a preliminary dispersion. Thereafter, the pre-dispersed liquid was supplied to an ultra apex mill (manufactured by Kotobuki Industries) equipped with a centrifugal separator filled with 75% 0.05 mmφ zirconia beads (manufactured by Neturen, YTZ balls), and dispersed for 3 hours at a rotational speed of 8 m / s. And a carbon black dispersion C-1 having a solid content concentration of 25% by weight and a colorant / resin (weight ratio) = 70/30 was obtained.

Preparation of Titanium Black Dispersion (T-1) The diffraction angle 2θ of the peak derived from the (200) plane of titanium nitride particles (Ti-Bk1, manufactured by Nissin Engineering Co., Ltd.) manufactured by the thermal plasma method is 42. The crystallite size determined from the half-width of this peak at 62 ° was 21.9 nm, and the BET specific surface area was 85.0 m ² / g. As a result of composition analysis, the titanium content was 70.4% by weight, the nitrogen content was 19.9% by weight, and the oxygen content was 8.86% by weight. Further, no X-ray diffraction peak attributed to TiO ₂ was observed.

  175 g of titanium nitride particles (Ti-Bk1), 107 g of a 35% by weight propylene glycol monoethyl ether acetate solution of acrylic polymer (P-1), 94 g of Dispersic LPN-21116 (manufactured by BYK Chemie) as a polymer dispersant Then, 624 g of propylene glycol monoethyl ether acetate was charged into a tank and stirred for 20 minutes with a homomixer (manufactured by PRIMIX) to obtain a preliminary dispersion. Thereafter, the pre-dispersed liquid was supplied to an ultra apex mill (manufactured by Kotobuki Industries) equipped with a centrifugal separator filled with 75% 0.05 mmφ zirconia beads (manufactured by Neturen, YTZ balls), and dispersed for 3 hours at a rotational speed of 8 m / s. And a titanium black dispersion T-1 having a solid content concentration of 25% by weight and a colorant / resin (weight ratio) = 70/30 was obtained.

Preparation of yellow pigment dispersion (Y-1) 120 g of organic pigment PY150 (Y-1, manufactured by LANXESS), 114 g of a 35% by weight propylene glycol monoethyl ether acetate solution of acrylic polymer (P-1), polymer dispersion Dispersic LPN-21116 (manufactured by Big Chemie) as an agent and 100 g of propylene glycol monoethyl ether acetate were charged into a tank and stirred for 20 minutes with a homomixer (manufactured by PRIMIX) to obtain a preliminary dispersion. Thereafter, the pre-dispersed liquid was supplied to an ultra apex mill (manufactured by Kotobuki Industries) equipped with a centrifugal separator filled with 75% 0.05 mmφ zirconia beads (manufactured by Neturen, YTZ balls), and dispersed for 3 hours at a rotational speed of 8 m / s And a yellow pigment dispersion Y-1 having a solid content concentration of 20% by weight and a colorant / resin (weight ratio) = 60/40 was obtained.

Preparation of Red Pigment Dispersion (R-1) Red Pigment Dispersion R-1 was prepared in the same manner as Yellow Pigment Dispersion Y-1, except that organic pigment PY254 (R-1, manufactured by BASF) was used as the pigment. Obtained.

Preparation of Blue Pigment Dispersion (B-1) Blue Pigment Dispersion B is the same as Yellow Pigment Dispersion Y-1, except that organic pigment PB15: 6 (B-1, manufactured by Toyo Ink) is used as the pigment. -1 was obtained.

Preparation of Green Pigment Dispersion (G-1) Green Pigment Dispersion G is the same as Yellow Pigment Dispersion Y-1, except that Green Pigment PG36 (G-1, manufactured by Dainichi Seika Kogyo Co., Ltd.) is used as the pigment. -1 was obtained.

Example 1
Carbon Black Dispersion C-1 (459.8 g), Yellow Pigment Dispersion Y-1 (17.6 g), and Red Pigment Dispersion R-1 (17.6 g) are mixed together to prepare an acrylic polymer (P-1). Propylene glycol monomethyl ether acetate 35% by weight solution (81.2 g), dipentaerythritol hexaacrylate (31.4 g) manufactured by Nippon Kayaku Co., Ltd. as a polyfunctional monomer, and ADEKA Co., Ltd. “Adeka Cruz” as photo radical polymerization initiator “NCI-831 (11.8 g), Shin-Etsu Chemical Co., Ltd. KBM503 (6.0 g) as an adhesion improver, a 10% by weight propylene glycol monomethyl ether acetate solution (3.0 g) of a silicone surfactant, Add a solution dissolved in propylene glycol monomethyl ether acetate (371.5 g) Solid content concentration of 20 wt% to obtain a black resin composition 1 the pigment / resin (weight ratio) = 45/55.

This black resin composition 1 was coated on a non-alkali glass AN100 substrate with a spinner 1H-DS manufactured by Mikasa Co., Ltd. and prebaked at 100 ° C. for 10 minutes to prepare a coating film. By using a mask aligner PEM-6M manufactured by Union Optical Co., Ltd., exposure (200 mJ / cm ² ) through a photomask, development using a 0.045 mass% KOH aqueous solution, and subsequent pure water cleaning, A patterned substrate was obtained. Furthermore, it was cured at 230 ° C. for 30 minutes. In this way, a black matrix 1 having a thickness of 1.00 μm was prepared.

Example 2
Carbon Black Dispersion C-1 (435.8 g), Yellow Pigment Dispersion Y-1 (35.3 g), and Red Pigment Dispersion R-1 (35.3 g) were mixed, and acrylic polymer (P-1) was mixed. Propylene glycol monomethyl ether acetate 35% by weight solution (78.9 g), Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate (31.2 g) as a polyfunctional monomer, ADEKA Co., Ltd. “Adeka Cruz” as photo radical polymerization initiator “NCI-831 (11.7 g), Shin-Etsu Chemical Co., Ltd. KBM503 (6.0 g) as an adhesion improver, a 10% by weight propylene glycol monomethyl ether acetate solution (3.0 g) of a silicone surfactant, Add a solution dissolved in propylene glycol monomethyl ether acetate (362.8 g) Solid content concentration of 20 wt%, to obtain a black resin composition 2 of pigment / resin (weight ratio) = 45/55.

  A black matrix 2 having a thickness of 1.00 μm was prepared using the black resin composition 2 in the same manner as in Example 1.

Example 3
Carbon Black Dispersion C-1 (387.7 g), Yellow Pigment Dispersion Y-1 (70.7 g), and Red Pigment Dispersion R-1 (70.7 g) are mixed together to prepare an acrylic polymer (P-1). Propylene glycol monomethyl ether acetate 35 wt% solution (74.4 g), dipentaerythritol hexaacrylate (30.8 g) manufactured by Nippon Kayaku Co., Ltd. as a polyfunctional monomer, and ADEKA Co., Ltd. “Adeka Cruz” as photo radical polymerization initiator “NCI-831 (11.6 g), KBE503 (6.0 g) manufactured by Shin-Etsu Chemical Co., Ltd. as an adhesion improver, a 10% by weight solution of propylene glycol monomethyl ether acetate (3.0 g) of a silicone surfactant, Add a solution dissolved in propylene glycol monomethyl ether acetate (345.3 g) Solid content concentration of 20 wt%, to obtain a black resin composition 3 of the pigment / resin (weight ratio) = 45/55.

  A black matrix 3 having a thickness of 1.00 μm was prepared using the black resin composition 3 in the same manner as in Example 1.

Example 4
Carbon Black Dispersion C-1 (339.4 g), Yellow Pigment Dispersion Y-1 (106.1 g), and Red Pigment Dispersion R-1 (106.1 g) were mixed, and acrylic polymer (P-1) Propylene glycol monomethyl ether acetate 35% by weight solution (69.8 g), dipentaerythritol hexaacrylate (30.4 g) manufactured by Nippon Kayaku Co., Ltd. as a polyfunctional monomer, and ADEKA Corporation “ADEKA CRUS as photo radical polymerization initiator “NCI-831 (11.4 g), KBE503 (6.0 g) manufactured by Shin-Etsu Chemical Co., Ltd. as an adhesion improver, a 10 wt% solution of propylene glycol monomethyl ether acetate (3.0 g) of a silicone surfactant, Add a solution dissolved in propylene glycol monomethyl ether acetate (32.77 g) Total solid concentration 20 wt%, to obtain a black resin composition 4 of the pigment / resin (weight ratio) = 45/55.

  A black matrix 4 having a thickness of 1.00 μm was prepared using the black resin composition 4 in the same manner as in Example 1.

Example 5
Carbon Black Dispersion C-1 (291.2 g), Yellow Pigment Dispersion Y-1 (141.5 g), and Red Pigment Dispersion R-1 (141.5 g) are mixed together to prepare an acrylic polymer (P-1). Propylene glycol monomethyl ether acetate 35% by weight solution (65.3 g), dipentaerythritol hexaacrylate (30.1 g) manufactured by Nippon Kayaku Co., Ltd. as a polyfunctional monomer, and ADEKA Co., Ltd. “Adeka Cruz” as photo radical polymerization initiator “NCI-831 (11.3 g), KBE503 (6.0 g) manufactured by Shin-Etsu Chemical Co., Ltd. as an adhesion improver, a 10% by weight solution of propylene glycol monomethyl ether acetate (3.0 g) of a silicone surfactant, Add a solution dissolved in propylene glycol monomethyl ether acetate (310.2 g) Total solid concentration 20 wt%, to obtain a black resin composition 5 of the pigment / resin (weight ratio) = 45/55.

  A black matrix 5 having a thickness of 1.00 μm was prepared using the black resin composition 5 in the same manner as in Example 1.

Comparative Example 9
Carbon Black Dispersion C-1 (242.9 g), Yellow Pigment Dispersion Y-1 (177.1 g), and Red Pigment Dispersion R-1 (177.1 g) were mixed together to prepare an acrylic polymer (P-1). Propylene glycol monomethyl ether acetate 35% by weight solution (60.7 g), dipentaerythritol hexaacrylate (29.7 g) manufactured by Nippon Kayaku Co., Ltd. as a polyfunctional monomer, and ADEKA Co., Ltd. “Adeka Cruz” as photo radical polymerization initiator "NCI-831 (11.1 g), Shin-Etsu Chemical Co., Ltd. KBM503 (6.0 g) as an adhesion improver, a 10% by weight propylene glycol monomethyl ether acetate solution (3.0 g) of a silicone surfactant, Add a solution dissolved in propylene glycol monomethyl ether acetate (292.5 g) Total solid concentration 20 wt%, to obtain a black resin composition 6 of pigment / resin (weight ratio) = 45/55.

  A black matrix 6 having a thickness of 1.00 μm was prepared using the black resin composition 6 in the same manner as in Example 1.

Comparative Example 7
A black resin composition 7 was obtained in the same manner as in Example 3 except that 106.1 g of the yellow pigment dispersion Y-1 and 35.3 g of the red pigment dispersion R-1 were used.

  Further, a black matrix 7 having a thickness of 1.00 μm was prepared using the black resin composition 7 in the same manner as in Example 1.

Example 8
A black resin composition 8 was obtained in the same manner as in Example 3 except that 35.3 g of the yellow pigment dispersion Y-1 and 106.1 g of the red pigment dispersion R-1 were used.

  Further, a black matrix 8 having a thickness of 1.00 μm was prepared using the black resin composition 8 in the same manner as in Example 1.

Example 9
A black resin composition 9 was obtained in the same manner as in Example 3 except that 310.2 g of the carbon black dispersion C-1 and 77.5 g of the titanium black dispersion T-1 were used.

  Further, a black matrix 9 having a thickness of 1.00 μm was prepared using the black resin composition 9 in the same manner as in Example 1.

Example 10
A black resin composition 10 was obtained in the same manner as in Example 3 except that 193.8 g of the carbon black dispersion C-1 and 193.9 g of the titanium black dispersion T-1 were used.

  Further, a black matrix 10 having a thickness of 1.00 μm was prepared using the black resin composition 10 in the same manner as in Example 1.

Comparative Example 8
Black resin composition 11 was obtained in the same manner as in Example 3 except that 77.5 g of carbon black dispersion C-1 and 310.2 g of titanium black dispersion T-1 were used.

  Further, a black matrix 11 having a thickness of 1.00 μm was prepared using the black resin composition 11 in the same manner as in Example 1.

Comparative Example 1
Carbon black dispersion C-1 (483.9 g), propylene glycol monomethyl ether acetate 35 wt% solution (83.4 g) of acrylic polymer (P-1), dipenta manufactured by Nippon Kayaku Co., Ltd. as a polyfunctional monomer Erythritol hexaacrylate (31.6 g), ADEKA Co., Ltd. “Adeka Cruz” NCI-831 (11.8 g) as a photoradical polymerization initiator, Shinetsu Chemical Co., Ltd. KBM503 (6.0 g) as an adhesion improver, A 10% by weight solution of propylene glycol monomethyl ether acetate (3.0 g) of a silicone-based surfactant was added to a solution of propylene glycol monomethyl ether acetate (380.2 g), and the total solid content concentration was 20% by weight. A black resin composition 12 having a resin (weight ratio) of 45/55 is obtained. .

  A black matrix 12 having a thickness of 1.00 μm was produced using the black resin composition 12 in the same manner as in Example 1.

Comparative Example 2
Black resin composition 13 was obtained in the same manner as in Example 2 except that 70.6 g of yellow pigment dispersion Y-1 was not added and red pigment dispersion R-1 was not added.

  Further, a black matrix 13 having a thickness of 1.00 μm was prepared using the black resin composition 13 in the same manner as in Example 1.

Comparative Example 3
A black resin composition 14 was obtained in the same manner as in Example 3 except that the yellow pigment dispersion Y-1 was 141.4 g and the red pigment dispersion R-1 was not added.

  Further, a black matrix 14 having a thickness of 1.00 μm was prepared using the black resin composition 14 in the same manner as in Example 1.

Comparative Example 4
A black resin composition 15 was obtained in the same manner as in Example 2 except that the red pigment dispersion R-1 was 70.6 g and the yellow pigment dispersion Y-1 was not added.

  Further, a black matrix 15 having a thickness of 1.00 μm was prepared using the black resin composition 15 in the same manner as in Example 1.

Comparative Example 5
A black resin composition 16 was obtained in the same manner as in Example 3 except that the blue pigment dispersion B-1 was added instead of the red pigment dispersion R-1.

  Further, a black matrix 16 having a thickness of 1.00 μm was prepared using the black resin composition 16 in the same manner as in Example 1.

Comparative Example 6
A black resin composition 17 was obtained in the same manner as in Example 3 except that the green pigment dispersion G-1 was added instead of the red pigment dispersion R-1.

  Further, a black matrix 17 having a thickness of 1.00 μm was prepared using the black resin composition 17 in the same manner as in Example 1.

  The evaluation results are shown in Table 1. It can be seen that the black matrix formed using the photosensitive resin composition shown in the examples shows a blue reflection color characteristic while having a high light shielding property, and further shows a high surface resistivity. On the other hand, the black matrix formed using the photosensitive resin composition shown in the comparative example has a high light-shielding property, but has a reflective color characteristic in which the a * value is large and yellow, or the b * value is large and red. I understand that. In addition, it can be seen that by setting the ratio of the black pigment in the light shielding material and the ratio of the yellow pigment in the non-black pigment to an appropriate range, more excellent reflection color characteristics can be exhibited while maintaining high light shielding properties.

  The photosensitive black resin composition of this invention can be utilized for the black matrix of the board | substrate for touchscreens.

Claims (10)

As at least a light shielding material, it contains (A) a black pigment and (B) a non-black pigment, (C) an alkali-soluble resin, (D) a polyfunctional acrylic monomer, (E) a photoradical polymerization initiator, and (F) A photosensitive black resin composition containing an organic solvent, wherein the weight ratio of the (A) black pigment to the total weight of the light-shielding material is 60% by weight to 95% by weight, and (A) A-1) Carbon black, (B) A non-black pigment, (B-1) a yellow pigment, and (B-2) a red pigment, and a film thickness of 1.0 μm on a non-alkali glass having a thickness of 0.7 mm. chromaticity of the reflected chromaticity of the resin black matrix was formed was measured from the non-alkali glass surface (a *, b *), characterized in Rukoto Do with a * ≦ 0.2 and b * ≦ 0 Photosensitive black resin composition. 2. The photosensitive black resin composition according to claim 1, wherein the weight ratio of (B-1) yellow pigment to the total weight of (B) non-black pigment is 30% by weight or more and 70% by weight or less. The photosensitive black resin composition according to claim 1 or 2, wherein the (B-1) yellow pigment is a yellow pigment selected from at least PY129, PY138, PY139, PY150, and PY185. The photosensitive black resin composition according to any one of claims 1 to 3, wherein the (B-2) red pigment is a red pigment selected from at least PR177, PR179, and PR254. The photosensitive black resin composition according to any one of claims 1 to 4, wherein the (A-1) carbon black is surface-modified with an organic group comprising a non-polymer group. The photosensitive black resin composition of any one of Claims 1-5 which contains (A-2) titanium nitride in addition to (A-1) carbon black as said (A) black pigment. The photosensitive black resin composition according to any one of claims 1 to 6, wherein a weight ratio of (A-1) carbon black to the total weight of the (A) black pigment is 50% by weight or more. It is an object for touch panels, The photosensitive black resin composition of any one of Claims 1-7. A resin black matrix substrate obtained by applying the black resin composition according to any one of claims 1 to 8 on a transparent substrate and forming a pattern thereon. A touch panel comprising the resin black matrix substrate according to claim 9.