JP2015001654A - Method for manufacturing laminate resin black matrix substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a laminate resin black matrix with high precision, which not only achieves a sufficient optical density in a thin film state but has a low reflectance, a high resistance value and high reliability.SOLUTION: A method for manufacturing a laminate resin black matrix substrate is provided, which includes steps of: forming a low optical density layer by applying a black resin composition (BM1) comprising (A1) a non-photosensitive alkali-soluble resin, (B1) a black pigment and (C1) a solvent on a transparent substrate; forming a high optical density layer by applying a black resin composition (BM2) comprising (A2) a photosensitive alkali-soluble resin, (B2) titanium nitride and/or titanium oxynitride, (C2) a solvent, (D) a photopolymerizable monomer and/or a photopolymerizable oligomer, and (E) a photopolymerization initiator having a specific structure on the low optical density layer; and forming a laminate resin black matrix by exposing and developing the layers of the low optical density layer and the high optical density layer.

Description

  The present invention relates to a method for producing a laminated resin black matrix substrate.

  The liquid crystal display device has a structure in which a liquid crystal layer is sandwiched between two substrates, and expresses light and dark using the electro-optic response of the liquid crystal layer, but color display is also possible by using a color filter substrate It is.

  Conventionally, a metal thin film made of a chromium-based material has been the mainstream of the black matrix formed on the color filter substrate, but a resin black matrix made of a resin and a black pigment has been developed to reduce costs and environmental pollution. . The resin black matrix is obtained by applying a black resin composition containing a resin and a black pigment such as carbon black on a substrate and drying it to form a black film, which is finely patterned into a lattice pattern by photolithography. . In order to easily form a resin black matrix, a photosensitive black resin composition in which carbon black is dispersed in a photosensitive acrylic resin is generally used (Patent Document 1), but it is difficult to achieve both photosensitivity and high light shielding properties. Therefore, in order to form a fine black matrix, there is a method in which a non-photosensitive black resin composition in which a black pigment such as carbon is dispersed is applied to a non-photosensitive polyimide resin, and then a photosensitive resist is applied and patterned (Patent Document 2). It is preferably used.

  On the other hand, a liquid crystal display device having a color filter substrate on which a resin black matrix containing a black pigment such as carbon black is formed is excellent in indoor visibility, but when used outdoors, it is derived from the black matrix. Deterioration of visibility due to external light reflection has been a problem.

  From such a background, various studies have been made to realize a resin black matrix having a high optical density (OD value) and a low reflectance when viewed from the transparent substrate side. Method of using black colorant fine particles coated on the surface (Patent Document 3), method of adding carbon black to titanium oxynitride (Patent Document 4), method of mixing titanium nitride and titanium carbide (Patent Document 5) A method of forming a two-layer structure of a colored relief layer and a black relief layer (Patent Document 6), a method of laminating a layer having a high optical density on a layer having a low optical density (Patent Document 7), and the like have been proposed. . Furthermore, as a method for accurately forming the laminated resin BM, a black non-photosensitive material layer is formed as a lower layer, a black photosensitive resist layer is laminated as an upper layer, and the black photosensitive resist layer is exposed and developed to form a black matrix. A method of batch processing is proposed (Patent Document 8).

Japanese Patent Laid-Open No. 10-300923 Japanese Patent No. 3196638 JP 2001-183511 A JP 2006-209102 A JP 2010-95716 A JP-A-8-146410 Japanese Patent No. 5209603 JP 10-73717 A

  However, since a highly light-shielding material has a high reflectance in principle, it has been extremely difficult to achieve both a sufficient optical density and a low reflectance in a single layer in the resin black matrix. On the other hand, when the resin black matrix has a two-layer structure, it is possible to achieve a low reflectance, but it is difficult to achieve a sufficiently high optical density with a thin film. However, no study has been made on a technique for processing a fine wire of 6 μm or less.

  Therefore, the present invention provides a manufacturing method for forming a highly reliable multilayer resin black matrix having a low reflectance and a high reliability while achieving a sufficient optical density with a thin film. The purpose is to provide.

  The present invention provides a method for producing a laminated resin black matrix substrate described in the following (1) to (6).

(1) A black resin composition (BM1) containing (A1) a non-photosensitive alkali-soluble resin, (B1) a black pigment, and (C1) a solvent is applied on a transparent substrate to form a low optical density layer. A low optical density layer forming step;
(A2) photosensitive alkali-soluble resin, (B2) titanium nitride and / or titanium oxynitride, (C2) solvent, (D) photopolymerizable monomer and / or photopolymerizable oligomer on the low optical density layer. And (E) a high optical density layer forming step of forming a high optical density layer by applying a black resin composition (BM2) containing a photopolymerization initiator having a structure represented by the following general formula (I) When,
A method of manufacturing a laminated resin black matrix substrate, comprising: a batch patterning step of exposing and developing the laminated low optical density layer and the high optical density layer to form a laminated resin black matrix.

(Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or CN, an alkyl group, an aryl group, and an aryl group. the hydrogen atoms of the alkyl group is further ^{oR 21, COR 21, SR 21} , NR 22 R 23, -NCOR 22 -OCOR 23, CN, halogen ^atom, -CR 21 ^{= CR} 22 ^{R 23} or ^-CO-CR 21 = ^{CR 22} R ²³ may be substituted, and R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a carbon atom. represents an aryl group or a heterocyclic group having 2 to 20 carbon atoms having 7 to 30, ^{R 2 represents R 11} or ^{oR 11, R 11} is a 1 to 20 carbon atoms Represents a kill group, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, wherein the hydrogen atom of the alkyl group, aryl group and arylalkyl group may be further substituted with a halogen atom. Well, R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and the above R ¹ , R ³ , R ²¹ , R The methylene group of the alkylene part of the substituent represented by ²² and R ²³ may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. The alkyl part of the substituent may have a branched side chain or a cyclic alkyl, and the alkyl terminal of the substituent is an unsaturated bond. Well, ^{R 3} is good .R ⁴ and ^{R 5} may form a ring together with the benzene ring adjacent each ^{independently} represent R ^{11, OR} 11, CN or a halogen atom, a and b is 0 to 3 independently.)

(2) The peak diffraction angle 2θ derived from the (200) plane of the titanium nitride particles when the black pigment (B2) is titanium nitride and CuKα rays are used as an X-ray source is 42.5 °. The method for producing a laminated resin black matrix substrate according to (1), which is 42.8 ° or less.
(3) The method for producing a laminated resin black matrix substrate according to (1) or (2), wherein the sum of the optical density of the low optical density layer and the optical density of the high optical density layer is 4.0 or more.
(4) The multilayer resin black matrix substrate according to any one of (1) to (3), wherein a total thickness of the low optical density layer and the high optical density layer is 1.5 μm or less. Production method.
(5) A color filter substrate in which red, green, or blue pixels are formed in openings of the laminated resin black matrix substrate formed by the method according to any one of (1) to (4).
(6) A liquid crystal display device in which a liquid crystal compound is filled between the color filter substrate according to (5) and a counter substrate.

  According to the method for producing a laminated resin black matrix substrate of the present invention, it is possible to realize a sufficient light shielding property so as not to transmit light from the backlight, and not only a high contrast and clear image is obtained but also a low reflectance. In addition, it is possible to easily obtain a high-definition liquid crystal display device that is extremely excellent in visibility even under external light and has high electrical reliability.

It is the schematic which shows one Embodiment of the manufacturing method of the multilayer resin black matrix substrate of this invention, and embodiment of a multilayer resin black matrix substrate.

  The present invention relates to a method for producing a resin black matrix (hereinafter referred to as “resin BM”) substrate having a laminated structure, and is used for forming a low optical density layer for producing a low-cost and stable laminated resin BM substrate. A method in which the resin composition (BM1) is applied on a transparent substrate and dried, and then a black resin composition (BM2) used for forming the high optical density layer is further applied to pattern both layers at once; In other words, it relates to the batch processing of the layers.

  The production method of the present invention includes a low optical density layer forming step of forming a low optical density layer by applying a black resin composition (BM1) on a transparent substrate, and a black resin on the low optical density layer. A high optical density layer forming step of applying a composition (BM2) to form a high optical density layer, and exposing and developing the laminated low optical density layer and the high optical density layer to obtain a laminated resin And a batch patterning process for forming a black matrix.

  After laminating the non-photosensitive resin layer and the photosensitive resin layer, the pattern is exposed and developed in a lump and patterned into fine lines. The balance between the development dissolution rate of the non-photosensitive resin layer and the development dissolution rate of the photosensitive resin layer is balanced. It is important to optimize. Specifically, compared with the case where the base is a non-soluble base material such as glass, the etching proceeds at the interface between the non-photosensitive resin layer and the photosensitive resin layer, so that the pattern is easily lost when processed into a thin line. Problem arises. In addition, when the photosensitive resin layer is a black resin layer, the surface of the coating film is sufficiently photocured, but the lower part of the coating film does not proceed with photocuring and develops and dissolves faster. How to increase it is more important.

  Accordingly, the inventors of the present invention have achieved high light-shielding properties with a thin film, and, as a result of intensive studies for patterning the thin-line laminated resin BM all together, the black resin composition (BM2) that forms the high optical density layer is obtained. (B2) It has been found that it is necessary to contain titanium nitride or titanium oxynitride as the black pigment, and further to contain a compound having a specific structure as the photopolymerization initiator (E).

  With the configuration of the present invention, it is possible to process the laminated resin BM having a thin line of 6 μm, although the optical density in the laminated state is as high as 4.0 or more. Furthermore, since it has high sensitivity not only for i-line (365 nm) but also for h-line (405 nm) as an exposure wavelength for patterning, a laminated BM substrate can be manufactured more easily.

When titanium nitride particles are used as the (B2) black pigment contained in the black resin composition (BM2), preferable characteristics will be described in detail. Here, the titanium nitride includes titanium nitride as a main component, and is usually low-order s titanium oxide and TiN _x that can be expressed as titanium oxide TiO ₂ and Ti _n O _2n-1 (1 ≦ n ≦ 20) as subcomponents. It contains titanium oxynitride represented by O _y (0 <x <2.0, 0.1 <y <2.0).

  The diffraction angle 2θ of the peak derived from the (200) plane when the CuKα ray of titanium nitride used in the present invention is an X-ray source is preferably 42.5 ° to 43.2 °, The angle is more preferably 42.5 ° to 42.8 °, and further preferably 42.5 ° to 42.7 °. By using titanium nitride particles having a diffraction angle θ in this range as a black pigment, it is possible to achieve a high OD value while keeping the black pigment concentration in the black resin composition low, and further, high ultraviolet rays. 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 titanium nitride particles can be obtained from the half 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: wavelength of X-ray (0.15418 nm), β _e : half width of diffraction peak, β _o : correction value of half width (0.12 °). However, β, β _e and β _o are calculated in radians.

  The crystallite size is preferably 10 nm or more, more preferably 10 to 50 nm, and even more preferably 10 to 30 nm. 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.

The specific surface area of the titanium nitride particles used in the present invention can be determined by the BET method, preferably 5 to 100 m ² / g as the value, 10 to 100 m ² / g and more preferably, 30 to 100 m ² / g is more preferable. 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 equivalent 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 at the time of dispersion, so that the dispersion stability tends to deteriorate, or when the resin black matrix is used, there is sufficient concealment as a black pigment. There is a problem that the OD value decreases 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)

The titanium nitride particles used in the present invention contain TiN as a main component, and are usually noticeable when oxygen is mixed during synthesis, especially when the particle size is small, but partly due to oxidation of the particle surface, etc. Contains oxygen atoms. 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 preferably 5 to 20% by mass, more preferably 8 to 20% by mass.

  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.

  A gas phase reaction method is generally used to synthesize titanium nitride, and examples include an electric furnace method and a thermal plasma method, but thermal plasma with little contamination, easy particle size, and high productivity. Synthesis by the method is preferred. Specifically, the primary particles of titanium nitride synthesized by the thermal plasma method are formed from almost single crystallites, and are lower by using titanium nitride synthesized by the thermal plasma method. This is preferable because a black matrix having a dielectric constant can be formed.

  Examples of the method for generating thermal plasma include direct current arc discharge, multiphase arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and high frequency plasma with less contamination of impurities from the electrode is more preferable. Specific methods for producing titanium nitride fine particles by the thermal plasma method include a method of reacting titanium tetrachloride and ammonia gas in a plasma flame (Japanese Patent Laid-Open No. 22221/1990), or evaporating titanium powder by high-frequency thermal plasma. A method of introducing nitrogen as a carrier gas and nitriding and synthesizing it in the cooling process (Japanese Patent Laid-Open No. 61-11140), a method of blowing ammonia gas into the peripheral edge of plasma (Japanese Patent Laid-Open No. 63-85007), and the like. However, the present invention is not limited to these, and the production method is not limited as long as titanium nitride particles having desired physical properties can be obtained. Various titanium nitride particles are commercially available, and a plurality of particles satisfying the diffraction angle and the oxygen atom amount defined in the present invention, and further satisfying the preferred crystallite size and specific surface area described above are also commercially available. ing. In the present invention, those commercially available products can be preferably used.

A preferable characteristic will be described in detail when titanium oxynitride is used as the (B2) black pigment contained in the black resin composition (BM2). Here, the titanium oxynitride refers to one that can be expressed by TiN _x O _y (0 <x <2.0, 0.1 <y <2.0). Generally, it is obtained by nitriding reduction of titanium oxide, and the production method is not limited, but JP-A-60-65069, JP-A-61-201610, and JP-A-2006-206871 It can be produced by the method described in Japanese Patent Publication No.

  As the black pigment (B2) contained in the black resin composition (BM2), a pigment other than titanium nitride or titanium oxynitride may be used as long as the optical density value does not decrease. Examples of such pigments include black organic pigments, mixed color organic pigments, and inorganic pigments. As the black organic pigment, for example, perylene black or aniline black is used, and as the mixed color organic pigment, for example, at least two kinds of pigments selected from red, blue, green, purple, yellow, magenta, cyan, etc. are mixed. Pseudo-blackened pigments include, for example, graphite or titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium or silver metal fine particles, metal oxides, composite oxides, metal sulfides. Or metal nitride.

  Conventionally, in the photosensitive black resin composition, since the photocuring of the lower part of the coating film does not proceed, there has been a problem that when the alkali development is performed, the lower part of the coating film is over-developed and a fine pattern is lost. Therefore, application of an oxime ester type carbazole initiator having high photosensitivity has been studied (Japanese Patent Laid-Open No. 2005-242279 and Japanese Patent No. 3754065). However, it was insufficient to achieve both a high light-shielding property such that the OD value per unit film thickness exceeds 3.5 and a fine wire workability of 5 μm in the laminated state.

  Specifically, since the light-shielding property per unit film thickness is high, when photocuring is advanced by increasing the amount of initiator added or increasing the exposure amount, curing only on the coating surface proceeds, so patterning This causes a problem that the shape of the BM is deteriorated.

  Therefore, it is important to use a compound having a structure represented by the following general formula (I) as the (E) photopolymerization initiator contained in the black resin composition (BM2).

（Ｉ）

(I)

(Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or CN, an alkyl group, an aryl group, and an aryl group. the hydrogen atoms of the alkyl group is further ^{oR 21, COR 21, SR 21} , NR 22 R 23, -NCOR 22 -OCOR 23, CN, halogen ^atom, -CR 21 ^{= CR} 22 ^{R 23} or ^-CO-CR 21 = ^{CR 22} R ²³ may be substituted, and R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a carbon atom. represents an aryl group or a heterocyclic group having 2 to 20 carbon atoms having 7 to 30, ^{R 2 represents R 11} or ^{oR 11, R 11} is a 1 to 20 carbon atoms Represents a kill group, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, wherein the hydrogen atom of the alkyl group, aryl group and arylalkyl group may be further substituted with a halogen atom. Well, R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and the above R ¹ , R ³ , R ²¹ , R The methylene group of the alkylene part of the substituent represented by ²² and R ²³ may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. The alkyl part of the substituent may have a branched side chain or a cyclic alkyl, and the alkyl terminal of the substituent is an unsaturated bond. Well, ^{R 3} is good .R ⁴ and ^{R 5} may form a ring taken together with the benzene ring adjacent each ^{independently} represent R ^{11, OR} 11, CN or a halogen atom, a and b is 0 to 3 independently.)

From the viewpoint of ease of synthesis, sensitivity, and solubility in a solvent, R ¹ in the general formula (I) is an alkyl group having 11 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or the number of carbon atoms. A 7-30 arylalkyl group is preferable, an aryl group having 6-30 carbon atoms is more preferable, and a substituted phenyl group is more preferable. Similarly, R ² in the general formula (I) is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably a methyl group. Also ^{R 3} in the general formula (I) is _preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms. Similarly, both a and b in the general formula (I) are preferably 0.

  By using the photopolymerization initiator having this structure in combination with a specific black pigment, that is, titanium nitride or titanium oxynitride, a coating film having a high optical density is used when the photosensitive black resin composition is exposed and patterned. In this case, photocuring proceeds to the deep part, and it becomes possible to process the fine BM with a good shape. In addition, processing with a low exposure amount is possible, and sufficient photocuring is possible not only in i-line (365 nm) but also in long-wavelength exposure such as h-line (405 nm), so that a laminated BM can be formed more easily. Is possible. In addition, the photopolymerization initiator itself of this structure is publicly known, and is described in Japanese Patent No. 4223071, and its production method is also described in this gazette. Furthermore, the photopolymerization initiator having this structure is already commercially available (for example, Adeka Cruz NCI-831 manufactured by ADEKA Corporation), and such a commercially available product can be preferably used in the present invention.

  In order to make the BM pattern shape better, it is more preferable to use a photopolymerization initiator other than the structure (I) and a chain transfer agent in combination.

  Other photopolymerization initiators are not particularly limited. For example, benzophenone compounds, acetophenone compounds, oxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, oxime ester compounds, carbazole compounds, triazines. Inorganic photopolymerization initiators such as system compounds, phosphorus compounds or titanates can be mentioned.

  More specifically, for example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, Benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone), 379 (2- (dimethylamino) -2-[(4-methylphenyl) methyl) ] -1- [4- ( -Morpholinyl) phenyl] -1-butanone), OXE01 (1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)]), OXE02 (ethanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)) CGI-113 (2- [4-methylbenzyl] -2-dimethylamino-1 -(4-morpholinophenyl) -butanone) or CGI-242 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl) Oxime); as described above, all manufactured by Ciba Specialty Chemicals Co., Ltd.), t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroant Quinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4- (p-methoxyphenyl) -2,6-di- (trichloromethyl)- Examples include ADEKA (registered trademark) Optomer N-1818 and N-1919, which are carbazole compounds manufactured by s-triazine or ADEKA Corporation, and Adeka Cruz NCI-930, which is an oxime ester compound.

  Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3 -Mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto- 2-butanol, mercapto Enol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopro Mercapto compounds such as pionate), disulfide compounds obtained by oxidizing the mercapto compound, iodinated alkyls such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Compounds.

  Examples of the alkali-soluble resin (A2) contained in the black resin composition (BM2) include an epoxy resin, an acrylic resin, a siloxane resin, and a polyimide resin. The heat resistance of the coating film and the storage stability of the composition are exemplified. Acrylic resin or polyimide resin is preferable.

  As the acrylic resin, for example, an acrylic resin having a carboxyl group is preferable, and a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is more preferable.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and vinyl acetic acid.

  Examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, N-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, acrylic acid n-pentyl, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate and other unsaturated carboxylic acid alkyl esters, styrene, p-methylstyrene , Aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene or α-methylstyrene, aminoalkyl esters of unsaturated carboxylic acids such as aminoethyl acrylate, glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate or glycidyl methacrylate, acetic acid Carboxylic acid vinyl esters such as vinyl and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene and isoprene, or acryloyl group or methacryloyl at each end Examples thereof include polystyrene having a group, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, or polybutyl methacrylate.

  More specifically, a quaternary copolymer of a monomer selected from the group consisting of methacrylic acid, acrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate and styrene is preferable, and the dissolution rate in an alkali developer Is more preferable, the average molecular weight (Mw) is 2,000 to 100,000 and the acid value is more preferably 70 to 150 (mgKOH / g).

  An acrylic resin having an ethylenically unsaturated group in the side chain is preferable because the sensitivity during exposure and development is improved. As the ethylenically unsaturated group, an acryl group or a methacryl group is preferable. The acrylic resin having an ethylenically unsaturated group in the side chain can be obtained, for example, by adding an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to the carboxyl group of an acrylic resin having a carboxyl group. it can.

  Examples of the acrylic resin having an ethylenically unsaturated group in the side chain include cyclomer (registered trademark) P (Daicel Chemical Industries, Ltd.) or alkali-soluble cardo resin, which is a commercially available acrylic resin. Average molecular weight (Mw) of 2,000 to 100,000 (measured by gel permeation chromatography using tetrahydrofuran as a carrier, and using a standard polystyrene calibration curve in order to make the solubility in a solvent or alkaline developer appropriate. The acid value is preferably 70 to 150 (mg KOH / g).

  The black resin composition (BM2) used for forming the high optical density layer contains (D) a photopolymerizable monomer or oligomer. Examples of the monomer or oligomer include polyfunctional or monofunctional acrylic monomers or oligomers. Examples of the polyfunctional acrylic monomer or oligomer include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, and 1,6-hexanediol (meth) adipic acid. Acrylic ester, phthalic anhydride propylene oxide (meth) acrylic ester, trimellitic acid diethylene glycol (meth) acrylic ester, rosin-modified epoxy di (meth) acrylate, alkyd-modified (meth) acrylate, full orange acrylate oligomer, tripropylene Glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimer Roll propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 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, -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, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, biscresol full orange acrylate or biscresol full orange methacrylate.

  By appropriately selecting and combining these polyfunctional or monofunctional acrylic monomers or oligomers, it is possible to control the sensitivity and processability during exposure and development. , Compounds having 3 or more functional groups are preferable, compounds having 5 or more functional groups are more preferable, and dipentaerythritol hexa (meth) acrylate or dipentaerythritol penta (meth) acrylate is more preferable.

  In order to improve the pattern shape of BM, in addition to dipentaerythritol hexa (meth) acrylate or dipentaerythritol penta (meth) acrylate, it has a fluorene ring that has many aromatic rings in its molecule and has high water repellency (meth) It is preferable to use acrylate together. The (meth) acrylate having a fluorene ring is preferably used in an amount of 90 to 40 parts by mass with respect to 10 to 60 parts by mass of dipentaerythritol hexa (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  The black resin composition (BM2) used for forming the high optical density layer may contain an adhesion improving agent in order to improve the adhesion to a glass plate or a silicon wafer. Examples of the adhesion improving agent include a silane coupling agent or a titanium coupling agent. The addition amount of the adhesion improving agent is generally about 0.2 to 20% by mass with respect to the alkali-soluble resin.

  The black resin composition (BM2) used for forming the high optical density layer may contain a polymer dispersant in order to improve the dispersion stability of the colorant. Examples of the polymer dispersant include a polyethyleneimine polymer dispersant, a polyurethane polymer dispersant, and a polyallylamine polymer dispersant. The addition amount of the polymer dispersant is generally about 1 to 40% by mass with respect to the colorant.

  The mass composition ratio of the colorant / resin component in the black resin composition (BM2) used for the formation of the high optical density layer is preferably in the range of 80/20 to 40/60. In order to balance the OD value, the range of 75/25 to 50/50 is more preferable. Here, the resin component refers to a polymer, a monomer, an oligomer, and a polymer dispersant contained in the photosensitive colored resin composition. If the resin component is too small, the adhesion of the resin BM to the substrate becomes poor. On the other hand, when the coloring material is too small, the optical density (OD value / μm) is lowered.

  As the (C2) solvent of the black resin composition (BM2), water or an organic solvent can be appropriately selected according to the dispersion stability of the colorant to be dispersed and the solubility of the resin component to be added. Examples of the organic solvent include esters, aliphatic alcohols, (poly) alkylene glycol ether solvents, ketones, amide polar solvents, or lactone polar solvents.

  Examples of the organic solvent when an acrylic resin is used as the alkali-soluble resin include diethylene glycol monobutyl ether acetate (boiling point 247 ° C.), benzyl acetate (boiling point 214 ° C.), ethyl benzoate (boiling point 213 ° C.), methyl benzoate (boiling point 200 ° C.). ), Diethyl malonate (boiling point 199 ° C.), 2-ethylhexyl acetate (boiling point 199 ° C.), 2-butoxyethyl acetate (boiling point 192 ° C.), ethylene glycol monobutyl ether acetate (boiling point 188 ° C.), diethyl oxalate (boiling point 185 ° C.) ), Ethyl acetoacetate (boiling point 181 ° C.), cyclohexyl acetate (boiling point 174 ° C.), 3-methoxy-butyl acetate (boiling point 173 ° C.), methyl acetoacetate (boiling point 172 ° C.), ethyl-3-ethoxypropionate 170 ° C. boiling point), 2-ethylbutyl acetate (boiling point 162 ° C.), isopentyl propionate (boiling point 160 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), pentyl acetate (boiling point 150 ° C.) or propylene glycol And monomethyl ether acetate (boiling point: 146 ° C .; hereinafter referred to as “PMA”).

  Examples of other solvents include ethylene glycol monomethyl ether (boiling point 124 ° C.), ethylene glycol monoethyl ether (boiling point 135 ° C.), propylene glycol monoethyl ether (boiling point 133 ° C.), diethylene glycol monomethyl ether (boiling point 193 ° C.). ), Monoethyl ether (boiling point 135 ° C.), methyl carbitol (boiling point 194 ° C.), ethyl carbitol (202 ° C.), propylene glycol monomethyl ether (boiling point 120 ° C.), propylene glycol monoethyl ether (boiling point 133 ° C.), propylene (Poly) alkylene glycol ether solvents such as glycol tertiary butyl ether (boiling point 153 ° C.) or dipropylene glycol monomethyl ether (boiling point 188 ° C.), ethyl acetate (boiling point 7 ° C), aliphatic esters such as butyl acetate (boiling point 126 ° C) or isopentyl acetate (boiling point 142 ° C), butanol (boiling point 118 ° C), 3-methyl-2-butanol (boiling point 112 ° C) or 3-methyl-3 -Aliphatic alcohols such as methoxybutanol (boiling point 174 ° C), ketones such as cyclopentanone or cyclohexanone, xylene (boiling point 144 ° C), ethylbenzene (boiling point 136 ° C) or solvent naphtha (petroleum fraction: boiling point 165 to 178) ° C).

  Furthermore, with the increase in the size of transparent substrates, application by a die coating apparatus has become mainstream. In order to achieve appropriate volatility and drying properties, the solvent has a boiling point of 150 to 200 ° C. and contains 30 to 75% by mass. A mixed solvent is preferred.

  The solid content concentration of the resin component in the black resin composition (BM2) (including components other than the solvent, including additives such as monomers, oligomers and photopolymerization initiators) and the colorant may be applied or dried. From a viewpoint of property, 2 to 30% is preferable and 5 to 20% is more preferable.

  The mixing ratio of each component in the black resin composition (BM2) is that (B2) titanium nitride and / or titanium oxynitride is usually 50 to 800 masses relative to 100 mass parts of (A2) photosensitive alkali-soluble resin. Parts, preferably 100 to 400 parts by weight, (C2) solvent is usually 300 to 9000 parts by weight, preferably 500 to 6000 parts by weight, (D) a photopolymerizable monomer and / or photopolymerizable oligomer is usually 25-400 mass parts, Preferably, it is 40-200 mass parts, (E) The photoinitiator is 2-90 mass parts normally, Preferably, it is 5-50 mass parts.

  Examples of the alkali-soluble resin (A1) contained in the black resin composition (BM1) include an epoxy resin, an acrylic resin, a siloxane polymer resin, or a polyimide resin, but the heat resistance of the coating film or the black resin composition An acrylic resin or a polyimide resin is preferable because of high storage stability, and a polyimide resin that is a non-photosensitive resin is more preferable because it is suitable for collectively forming a low optical density layer and a high optical density layer. Here, the polyimide resin includes, in addition to a polyimide resin having a completely closed ring structure, a polyamic acid resin that is a precursor of a polyimide resin having a completely closed ring structure and a polyimide resin in which a part of the polyamic acid resin is closed.

  A polyimide resin can be preferably used as a non-photosensitive resin, and is formed by heat-opening imidization of a polyamic acid as a precursor. The polyamic acid resin is generally obtained by addition polymerization of a compound having an acid anhydride group and a diamine compound at 40 to 100 ° C., and has a repeating structural unit represented by the following general formula (5). The polyimide resin in which the polyamic acid resin is partially closed includes an amic acid structure represented by the following general formula (6), a structure represented by the following general formula (7) in which the amic acid structure is partially imide ring-closed, and And an amide structure represented by the following general formula (8), in which the amic acid structure is all ring-closed with the imide.

In the general formulas (5) to (8), R ⁶ represents a trivalent or tetravalent organic group having 2 to 22 carbon atoms, R ⁷ represents a divalent organic group having 1 to 22 carbon atoms, and n Represents an integer of 1 or 2. Here, as each organic group, the organic group which the aromatic tetracarboxylic acid which comprises a polyimide gives the preferable aromatic tetracarboxylic dianhydride mentioned later is preferable.

  In order to improve the heat resistance and insulation of the polyimide resin, the diamine compound used for obtaining the polyamic acid resin is preferably an aromatic diamine compound, and the compound having an acid anhydride group is preferably an acid dianhydride.

  Examples of the aromatic diamine compound include paraphenylene diamine, metaphenylene diamine, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 1,3-bis (4-aminophenoxy) benzene, 1 , 4-bis (4-aminophenoxy) benzene, 2,2-bis (trifluoromethyl) benzidine, 9,9'-bis (4-aminophenyl) fluorene 4,4'-diaminodiphenylamine, 3,4'- Diaminodiphenylamine, 3,3′-di Minodiphenylamine, 2,4'-diaminodiphenylamine, 4,4'-diaminodibenzylamine, 2,2'-diaminodibenzylamine, 3,4'-diaminodibenzylamine, 3,3'-diaminodibenzylamine N, N′-bis- (4-amino-3-methylphenyl) ethylenediamine, 4,4′-diaminobenzanilide, 3,4′-diaminobenzanilide, 3,3′-diaminobenzanilide, 4,3 '-Diaminobenzanilide, 2,4'-diaminobenzanilide, N, N'-p-phenylenebis-p-aminobenzamide, N, N'-p-phenylenebis-m-aminobenzamide, N, N'- m-phenylenebis-p-aminobenzamide, N, N′-m-phenylenebis-m-aminobenzamide, N, N ′ Dimethyl-N, N′-p-phenylenebis-p-aminobenzamide, N, N′-dimethyl-N, N′-p-phenylenebis-m-aminobenzamide, N, N′-diphenyl-N, N ′ -P-phenylenebis-p-aminobenzamide or N, N'-diphenyl-N, N'-p-phenylenebis-m-aminobenzamide, but paraphenylenediamine, metaphenylenediamine, 3,3'- Diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 9,9′-bis (4-aminophenyl) fluorene Alternatively, 4,4′-diaminobenzanilide is preferable.

  Examples of the aromatic tetracarboxylic acid include 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,4, 9,10-perylenetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1 , 2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-paraterphenyltetracarboxylic dianhydride or 3,3 ′, 4,4′-metaterphenyltetracarboxylic Examples thereof include acid dianhydrides, and 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-benzophenone tetracarboxylic dianhydride or pyromellitic dianhydride is preferable. When a fluorine-based tetracarboxylic dianhydride such as 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride is used, a polyimide having good transparency in a short wavelength region can be obtained. .

  In addition polymerization of a compound having an acid anhydride group and a diamine compound to obtain a polyamic acid resin, an acid anhydride such as maleic anhydride or phthalic anhydride is added as a terminal blocking agent as necessary. It doesn't matter. Moreover, in order to improve adhesiveness with inorganic substances, such as a glass plate or a silicon wafer, you may use Si type acid anhydride or Si type diamine. As the Si-based diamine, a siloxane diamine such as bis-3- (aminopropyl) tetramethylsiloxane is preferable. The proportion of siloxane diamine in the total diamine is preferably 1 to 20 mol%. When the siloxane diamine is less than 1 mol%, the adhesiveness is not sufficiently improved. On the other hand, when it exceeds 20 mol%, problems such as a decrease in heat resistance and a remaining film during alkali development due to excessive adhesion occur.

  As the compound having an acid anhydride group and the diamine compound for obtaining a polyamic acid resin, an alicyclic acid dianhydride or an alicyclic diamine may be used. Examples of the alicyclic acid dianhydride or alicyclic diamine include 1,2,4,5-cyclohexanetetracarboxylic dianhydride and bicyclo [2.2.2] oct-7-ene-2. , 3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2-endo-3-endo-5-exo-6-exo-2,3,5,6-tetracarboxylic Acid dianhydride, bicyclo [2.2.1] heptane-2-exo-3-exo-5-exo-6-exo-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2. 2.1] heptane-2,3,5,6-tetracarboxylic dianhydride or decahydro-dimethananaphthalene tetracarboxylic dianhydride or bis [2- (3-aminopropoxy) ethyl] ether, 4-Butanediol-bis (3-a Nopropyl) ether, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro-5,5-undecane, 1,2-bis (2-aminoethoxy) ethane, 1,2 -Bis (3-aminopropoxy) ethane, triethylene glycol-bis (3-aminopropyl) ether, polyethylene glycol-bis (3-aminopropyl) ether, 3,9-bis (3-aminopropyl) -2,4 , 8,10-tetraspiro-5,5-undecane or 1,4-butanediol-bis (3-aminopropyl) ether.

  The (B1) black pigment contained in the black resin composition (BM1) is not particularly limited, and examples thereof include carbon black, titanium black, chromium oxide, iron oxide, aniline black, perylene pigment, and C.I. I. Examples thereof include black pigments such as Solvent Black 123, or inorganic black pigments such as carbon black, titanium, manganese, iron, copper, or cobalt composite oxide coated with resin, or a combination of an organic pigment and a black pigment. Carbon black, titanium nitride, or titanium oxynitride is preferable because of its high light shielding properties.

  Examples of the (C1) solvent contained in the black resin composition (BM1) include esters, aliphatic alcohols, (poly) alkylene glycol ether solvents, ketones, N-methyl-2-pyrrolidone, N, N Examples include amide polar solvents such as dimethylacetamide or N, N-dimethylformamide or lactones, but lactones or mixed solvents containing lactones as main components are preferred in order to enhance the dispersion effect of pigments that are black pigments. . Here, the solvent containing lactones as a main component refers to a solvent having a maximum mass ratio of lactones in all solvents. The lactone refers to an aliphatic cyclic ester compound having 3 to 12 carbon atoms. Examples of lactones include β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone. From the viewpoint of solubility of the polyimide precursor, γ- Butyrolactone is preferred. Examples of solvents other than lactones include 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, propylene glycol mono-methyl ether, propylene glycol mono-methyl ether acetate, Dipropylene glycol-mono-methyl ether, tripropylene glycol-mono-methyl ether, propylene glycol-mono-tertiary-butyl ether, isobutyl alcohol, isoamyl alcohol, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, butyl cellosolve acetate, methyl carbitol, Examples include methyl carbitol acetate, ethyl carbitol or ethyl carbitol acetate.

  Furthermore, with the increase in the size of transparent substrates, application by a die coating apparatus has become mainstream. In order to achieve appropriate volatility and drying properties, the solvent has a boiling point of 150 to 200 ° C. and contains 30 to 75% by mass. A mixed solvent is preferred.

  The mixing ratio of each component in the black resin composition (BM1) is such that (B1) black pigment is usually 10 to 150 parts by mass, preferably 15 to 100 parts by mass of (A1) non-photosensitive alkali-soluble resin. 75 parts by mass and (C1) solvent are 250 to 4000 parts by mass, preferably 300 to 3000 parts by mass.

  The black resin composition (BM1) and the black resin composition (BM2) may contain a surfactant in order to prevent Benard cell while ensuring applicability and smoothness of the black film. 0.001-10 mass% is preferable with respect to a coloring material, and, as for the addition amount of surfactant, 0.01-1 mass% is more preferable.

  Examples of the surfactant include an anionic surfactant such as ammonium lauryl sulfate or polyoxyethylene alkyl ether sulfate triethanolamine, a cationic surfactant such as stearylamine acetate or lauryltrimethylammonium chloride, lauryldimethylamine oxide, or lauryl. Amphoteric surfactants such as carboxymethylhydroxyethylimidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or sorbitan monostearate, and silicone-based interfaces mainly composed of polydimethylsiloxane An activator or a fluorosurfactant is mentioned.

  The proportion of the (B1) black pigment in the total solid content of the black resin composition (BM1) is preferably 5 to 80% by mass, and more preferably 10 to 50% by mass. (B1) When the ratio of the black pigment is less than 5% by mass, it is difficult to obtain a sufficient optical density. On the other hand, when it exceeds 80 mass%, patterning will become difficult. Here, the total solid content means all the components except the solvent among the components contained in the black resin composition.

  As a manufacturing method of a black resin composition (BM1) and a black resin composition (BM2), for example, a method of dispersing a pigment directly in a resin solution using a disperser, or water or an organic solvent using a disperser A method of preparing a pigment dispersion by dispersing the pigment therein and then mixing the pigment dispersion and the resin solution can be mentioned. Examples of the pigment dispersion method include a ball mill, a sand grinder, a three-roll mill, and a high-speed impact mill. From the viewpoint of dispersion efficiency and fine dispersion, a bead mill is preferable. Examples of the bead mill include a coball mill, a basket mill, a pin mill, and a dyno mill. As beads of the bead mill, for example, titania beads, zirconia beads, or zircon beads are preferable. The bead diameter used for dispersion is preferably 0.01 to 5.0 mm, and more preferably 0.03 to 1.0 mm. When the primary particle diameter of the pigment or the secondary particles formed by agglomeration of the primary particles is small, the bead diameter used for dispersion is preferably a fine dispersed bead such as 0.03 to 0.10 mm. In this case, it is preferable to disperse using a bead mill having a separator by a centrifugal separation method capable of separating fine dispersed beads and a dispersion. On the other hand, when a pigment containing coarse particles of about submicron is dispersed, dispersed beads having a bead diameter of 0.10 mm or more are preferable in order to obtain a sufficient grinding force.

  The color filter substrate of the present invention is characterized in that red, green or blue pixels are formed in the opening of the laminated resin BM substrate of the present invention. The liquid crystal display device of the present invention is characterized in that a liquid crystal compound is filled between the color filter substrate of the present invention and the counter substrate.

  The laminated batch processing of the laminated resin BM substrate of the present invention will be described in more detail.

  Examples of the transparent substrate include quartz glass, borosilicate glass, aluminosilicate glass, inorganic glass such as soda lime glass whose surface is silica-coated, or an organic plastic film or sheet.

  Examples of a method for applying a non-photosensitive black resin composition used for forming a low optical density layer on a transparent substrate include, for example, a spin coater, a bar coater, a blade coater, a roll coater, a die coater, a screen printing method, and a black transparent substrate. Examples include a method of immersing in a resin composition or a method of spraying a black resin composition on a substrate.

  The coating film obtained by coating the non-photosensitive black resin composition on the transparent substrate is dried and cured by air drying, heat drying, vacuum drying, or the like to form a dry film. As heating conditions, the heating temperature and time depend on the composition of the non-photosensitive black resin composition and the thickness formed, but are preferably 80 to 200 ° C, more preferably 100 to 150 ° C. It is preferable to heat for 60 minutes. When the heating temperature is less than 80 ° C., a photosensitive black resin composition for forming a high optical density layer is applied in the next step without being cured, and defects such as cracks and expansion order dissolution occur in the coating film. In some cases, if the temperature is higher than 200 ° C., curing proceeds too much, and patterning in a later step may be difficult. Moreover, in order to suppress drying unevenness or conveyance unevenness, the transparent substrate coated with the non-photosensitive black resin composition can be dried under reduced pressure with a vacuum dryer equipped with a heating device and then heated to be semi-cured (semi-cured). preferable. In this case, the drying under reduced pressure is preferably performed by using heating on a hot plate and drying under reduced pressure. In this case, the heating condition is preferably 25 ° C to 80 ° C, and more preferably 30 ° C to 60 ° C. Further, the ultimate pressure in this case is preferably a reduced pressure condition of 10 to 200 Pa, and more preferably a reduced pressure condition of 30 to 100 Pa.

  Next, the photosensitive black composition used for formation of a high optical density layer is apply | coated on said dry film, and it is dried. About the application | coating, drying, and heating conditions in this case, it is preferable to adjust suitably with the composition and formed thickness of the photosensitive black resin composition similarly to a nonphotosensitive black resin composition.

Thereafter, pattern exposure is performed by irradiating ultraviolet rays from an exposure apparatus through a photomask corresponding to a desired pattern. Examples of lamps that can be used in the exposure process include ultra high pressure mercury lamps, chemical lamps, high pressure mercury lamps, low pressure mercury lamps, and ultraviolet LED lamps. Exposure is represented by the time-integrated value of the irradiance, but are not particularly limited, for example, with respect to 365nm ^wavelength, it is preferable to irradiate at ^{10mJ / cm 2 ~1000mJ / cm 2} , 20mJ / cm Irradiation at ^{2 to} 200 mJ / cm ² is more preferable. As the alkaline developer, an alkaline developer to which 0.01 to 1% by mass of a surfactant such as a nonionic surfactant is added is preferable.

  Subsequent to exposure, development is performed with an alkaline developer to form a BM pattern. Although it does not specifically limit as an alkaline substance which can be used, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, etc. Primary amines, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), choline Quaternary ammonium salts such as triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol, and other alcohol amines, pyrrole, piperidine, 1,8-diazabicyclo [5, And organic alkalis such as cyclic amines such as 4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, morpholine. Among these, since the solubility of the coating film is good and the problem of odor is small, an aqueous developer of an alkaline aqueous solution is preferable and contains sodium hydroxide and / or sodium carbonate, potassium hydroxide and / or potassium carbonate or TMAH. Is preferred. The concentration of the alkaline substance can be used in the range of 0.01% by mass to 50% by mass. Furthermore, it is preferable to use an alkaline developer to which 0.01 to 1% by mass of a surfactant such as a nonionic surfactant is added because a better pattern can be obtained. Alkali development can be performed by dip development, shower development, paddle development, ultrasonic development, or the like, and these may be combined. In shower development, the shower pressure is preferably adjusted so as to obtain an optimal pixel shape, and the shower pressure is preferably 0.05 to 5 MPa. After the development, a washing step with pure water or the like may be appropriately added to remove the alkali developer. The development conditions are preferably 20 ° C. to 30 ° C. and 10 seconds to 120 seconds.

  The obtained pattern of the laminated state becomes a laminated resin BM patterned by subsequent heat treatment. The heat treatment of the laminated pattern is preferably performed continuously or stepwise at 150 to 300 ° C. for 0.25 to 5 hours, for example, in air, nitrogen, or vacuum. The temperature of the heat treatment is more preferably 180 to 250 ° C.

  The film thickness of the low optical density layer and the high optical density layer in the laminated resin BM substrate of the present invention is preferably 0.3 to 1.2 μm, and more preferably 0.4 to 1.0 μm. Moreover, 0.5-2.0 micrometers is preferable and, as for the film thickness of the whole laminated resin BM which combined both layers, 1.0-1.5 micrometers is more preferable. When the entire film thickness is less than 0.5 μm, an appropriate optical density cannot be obtained. On the other hand, if it exceeds 2.0 μm, it causes a decrease in contrast due to poor liquid crystal alignment.

  The optical density (optical density, hereinafter referred to as “OD value”) of the entire laminated resin BM formed on the laminated resin BM substrate of the present invention is preferably 3 or more, more preferably 4 to 5 in the visible light region with a wavelength of 380 to 700 nm. preferable. If the overall OD value is less than 3, part of the light from the backlight is transmitted, causing a reduction in contrast. On the other hand, when it exceeds 5, the addition amount of the black pigment increases and the reflectance tends to be relatively high.

  The OD value of the low optical density layer is preferably 0.5 to 2.0, and more preferably 0.8 to 1.5. The OD value of the high optical density layer is preferably 1.5 to 5.0, more preferably 2.0 to 3.5.

  Examples of the pattern shape of the laminated resin BM formed on the laminated resin BM substrate of the present invention include a rectangle, a stripe, a square, a polygon, a corrugated shape, and an uneven shape. The width of the pattern is preferably 3 to 30 μm, more preferably 3 to 10 μm, and further preferably 3 to 6 μm. When the pattern width exceeds 30 μm, the aperture area of the pixel is reduced and the luminance is lowered. On the other hand, if it is less than 3 μm, it may be lost during processing.

  The pattern of the low optical density layer and the pattern of the high optical density layer constituting the laminated resin BM substrate of the present invention are preferably substantially the same in order to maximize the aperture area of the pixel and improve the luminance. Here, “substantially the same” means that the pattern shapes such as rectangles or stripes are the same, and the pattern widths need not be exactly the same, but the pattern width of the low optical density layer and the pattern width of the high optical density layer Is preferably 3 μm or less, more preferably 1 μm or less, and even more preferably 0.5 μm or less.

The surface resistance value (Ω / □) of the laminated resin BM formed on the laminated resin BM substrate of the present invention is preferably 10 ⁸ (Ω / □) or more, and more preferably 10 ¹⁵ (Ω / □) or more. By forming the laminated resin BM having a large surface resistance value, the insulation property of the color filter substrate is increased, and the electric field is not disturbed when a voltage is applied, and the liquid crystal display has a good liquid crystal orientation with a good liquid crystal orientation. A device can be obtained.

  The laminated resin BM substrate of the present invention can be used for electronic materials, various displays, and the like, taking advantage of its high OD and low reflection characteristics, plasma display panel (PDP) partition walls, dielectric patterns, electrodes (conductors) Circuit) pattern or a wiring pattern of an electronic component, etc. Among them, in order to improve the display characteristics of a color filter used in a color liquid crystal display device or the like, the resin BM is suitable as a resin BM substrate provided on the interval portion and the peripheral portion of the coloring pattern and the outside light side of the TFT. The color filter substrate of the present invention is characterized in that red, green or blue pixels are formed in the opening of the laminated resin BM substrate of the present invention.

  As a method for producing a color filter substrate of the present invention, for example, after forming a laminated resin BM on a transparent substrate, the color selectivity of red (R), green (G) or blue (B) is obtained by a known method. There is a method of forming a pixel and forming an overcoat film thereon as necessary. Examples of the overcoat film include an epoxy film, an acrylic epoxy film, an acrylic film, a siloxane polymer film, a polyimide film, a silicon-containing polyimide film, and a polyimidesiloxane film. A transparent conductive film may be further formed on the overcoat film. As a transparent conductive film, oxide thin films, such as ITO, are mentioned, for example. Examples of a method for producing an ITO film having a thickness of about 0.1 μm include a sputtering method and a vacuum evaporation method. Examples of the material of the pixel include an inorganic film whose film thickness is controlled so as to transmit only arbitrary light, or a colored resin film in which dyeing, dye dispersion, or pigment dispersion is performed.

  As the pigment dispersed in the pixels of the color filter substrate of the present invention, those excellent in light resistance, heat resistance and chemical resistance are preferable.

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275 or 276. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254 is preferred, and C.I. I. Pigment Red 177, 209, 224, 242 or 254 is more preferable.

  Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. I. Pigment Green 7, 36 or 58 is preferable.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207 or 208, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 is preferable. I. Pigment Yellow 83, 138, 139, 150 or 180 is more preferable.

  Examples of the orange pigment include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 or 79. I. Pigment Orange 38 or 71 is preferred.

  Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78 or 79. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 or 60 is preferable. I. Pigment Blue 15: 6 is more preferable.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49 or 50. I. Pigment Violet 19 or 23 is preferred, and C.I. I. Pigment Violet 23 is more preferable.

  These pigments may be subjected to surface treatment such as rosin treatment, acidic group treatment or basic treatment, if necessary, and a pigment derivative may be added as a dispersant.

  When the pixel of the color filter substrate of the present invention is a colored resin film in which a pigment is dispersed, examples of the binder resin used for the formation include acrylic resin, polyvinyl alcohol, polyamide, or polyimide. From the viewpoint of chemical properties, polyimide is preferable.

  The color filter substrate of the present invention may form a fixed spacer. The fixed spacer refers to a spacer that is fixed at a specific location on the color filter substrate and contacts the counter substrate when a liquid crystal display device is manufactured. Thus, a certain gap is maintained between the counter substrate and the liquid crystal compound is filled between the gaps. By forming the fixed spacer, it is possible to omit the step of dispersing the spherical spacer in the manufacturing process of the liquid crystal display device and the step of kneading the rod-shaped spacer in the sealing agent.

  The liquid crystal display device of the present invention is characterized in that a liquid crystal compound is filled between the color filter substrate of the present invention and a counter substrate.

  In the above description, each component can be used alone or in combination of two or more unless the context clearly indicates otherwise.

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

<Evaluation method>
[OD value]
A resin BM having a desired film thickness is formed on an alkali-free glass having a thickness of 0.7 mm, and the intensity of each of incident light and transmitted light is measured using a microspectroscope (MCPD2000; manufactured by Otsuka Electronics Co., Ltd.). Calculated from (9).
OD value = log ₁₀ (I ₀ / I) (9)
I ₀ : Incident light intensity I: Transmitted light intensity

[Reflectance]
A laminated resin BM having a desired film thickness is formed on an alkali-free glass having a thickness of 0.7 mm, and an ultraviolet-visible spectrophotometer (UV-2450; manufactured by Shimadzu Corporation) is used at an incident angle of 5 ° from the glass surface. The absolute reflection measurement of was measured. From the obtained spectrum, Y (reflectance) at the D65 light source calculated by the CIE XYZ color system was calculated.

[Surface resistance value]
Using Hiresta UP MCP-HT450 (manufactured by Mitsubishi Chemical Analytech), the surface resistance value (Ω / □) was measured at an applied voltage of 10 V, and the insulation was determined based on the following criteria.
○: More than the measurement limit (10 ¹⁵ Ω / □ or more) and extremely high insulation Δ: 10 ⁸ Ω / □ or more and less than 10 ¹⁵ Ω / □ and sufficient insulation ×: 10 ⁸ Ω / □ Less than that and insulation is insufficient

[Thin wire workability]
About the fine line pattern (5 micrometers and 10 micrometers) formed on the board | substrate, the edge of the pattern was observed with the microscope and it evaluated as follows.
○: Pattern with no missing pattern and good linearity with no gap Δ: No pattern missing, but with missing pattern with poor linearity ×: Pattern missing

[sensitivity]
Using the h-line titler device (TNT-E150F / 2, manufactured by Toray Engineering Co., Ltd.), the minimum exposure amount required to form a pattern having a line width of 50 μm on the substrate was measured and evaluated as follows.
○: 250mJ / cm ² less than in patternable △: 250mJ / cm ² or more 500 mJ / cm ² less than in patternable ×: 500mJ / cm ² or more even pattern formation impossible

<Production example>
(Synthesis of polyamic acid A-1)
4,4′-diaminophenyl ether (0.30 molar equivalent), paraphenylenediamine (0.65 molar equivalent), bis (3-aminopropyl) tetramethyldisiloxane (0.05 molar equivalent), γ-butyrolactone 850 g And 850 g of N-methyl-2-pyrrolidone were added, 3,3 ′, 4,4′-oxydiphthalcarboxylic dianhydride (0.9975 molar equivalent) was added, and the mixture was reacted at 80 ° C. for 3 hours. . Furthermore, maleic anhydride (0.02 molar equivalent) was added and reacted at 80 ° C. for 1 hour to obtain a polyamic acid A-1 (polymer concentration 20% by mass) solution.

(Synthesis of polyamic acid A-2)
4,4′-diaminophenyl ether (0.95 molar equivalent), bis (3-aminopropyl) tetramethyldisiloxane (0.05 molar equivalent) and 1700 g (100%) of γ-butyrolactone were charged, Anhydride (0.49 molar equivalent) and benzophenonetetracarboxylic dianhydride (0.50 molar equivalent) were added and reacted at 80 ° C. for 3 hours. Furthermore, maleic anhydride (0.02 molar equivalent) was added and further reacted at 80 ° C. for 1 hour to obtain a polyamic acid A-2 (polymer concentration 20 mass%) solution.

(Synthesis of acrylic polymer (P-1))
After synthesizing methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30/40/30) by the method described in the literature (Japanese Patent No. 3120476; Example 1), 40 parts by mass of glycidyl methacrylate is added and purified. By reprecipitation with water, filtration and drying, an acrylic polymer (P-1) powder having an average molecular weight (Mw) of 40,000 and an acid value of 110 (mgKOH / g) was obtained.

(B1) Black pigment or (B2) Black pigment Bk-1: Titanium nitride particles (Nisshin Engineering)
Bk-2: Titanium nitride particles (manufactured by HEFEI KAIER NANOMETER)
Bk-3: Titanium nitride particles (50 nm, manufactured by Wako Pure Chemical Industries, Ltd.)
Bk-4: Titanium oxynitride particles (13M-T, manufactured by Mitsubishi Materials Electronic Chemicals)
Bk-5: Titanium oxynitride particles (13M-C, manufactured by Mitsubishi Materials Electronic Chemicals)
Bk-6: Carbon black (TPX-1291, manufactured by Cabot Corporation)
Table 1 shows the physical properties of the titanium nitride particles and titanium oxynitride particles.

(E) Photopolymerization initiator (e-1) NCI-831 (manufactured by ADEKA): Refer to the following structural formula

(E-2) OXE02 (manufactured by BASF): ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)

(E-3) N1919 (made by ADEKA): Refer to the following structural formula

(E-4) OXE01 (manufactured by BASF): 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]

Example 1
(B1) Titanium oxynitride particles Bk-4 (96 g), polyamic acid solution A-1 (120 g), γ-butyrolactone (114 g), N-methyl-2pyrrolidone (538 g) and 3 methyl-3 methoxybutyl as a black pigment Ultra apex mill equipped with a centrifugal separator charged with acetate (132 g) in a tank, stirred for 1 hour with a homomixer (manufactured by Special Machine), and filled with 70% 0.05 mmφ zirconia beads (YTZ balls; manufactured by Nikkato) Was used for 2 hours at a rotational speed of 8 m / s to obtain a black pigment dispersion DB1-1 having a solid content concentration of 12% by mass and a pigment / resin (mass ratio) of 80/20.

  To black pigment dispersion Bk1 (364 g), polyimide resin A-1 (281 g), γ-butyrolactone (140 g), N-methyl-2-pyrrolidone (148 g), 3 methyl-3 methoxybutyl acetate (66 g) and surface activity Agent LC951 (1 g; manufactured by Enomoto Kasei) was added to obtain a black resin composition (BM1) -1 having a total solid concentration of 10% by mass and a black pigment / resin (mass ratio) of 35/65.

  (B2) Dispersic LPN- having 200 g of titanium nitride particles Bk-1 as a black pigment, 114 g of a 35 mass% PMA solution of acrylic polymer (P-1), and a tertiary amino group and a quaternary ammonium salt as a polymer dispersant A tank was charged with 25 g of 21116 and 661 g of PMA, and stirred with a homomixer for 20 minutes 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, and dispersed at a rotational speed of 8 m / s for 3 hours to obtain a solid concentration of 25 A black pigment dispersion DB1-2 having a mass% of colorant / resin (mass ratio) = 80/20 was obtained.

  To 35.31 g of PMA, 0.35 g of Adeka Arcles (registered trademark) NCI-831 which is e-1 as a photopolymerization initiator was added and stirred until the solid content was dissolved.

  Furthermore, 5.55 g of a 35% by weight PMA solution of acrylic polymer (P-1), 2.81 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, and KBM5103 (Shin-Etsu) as an adhesion improver 0.60 g of Chemical Co., Ltd.) and 0.40 g of a PMA 10 mass% solution of a silicone surfactant BYK333 as a surfactant were added and stirred at room temperature for 1 hour to obtain a photosensitive resist. Black resin composition (BM2) -1 having a total solid content concentration of 20% and black pigment / resin (mass ratio) = 58/42 by adding 56.98 g of black pigment dispersion DB1-2 to this photosensitive resist Was prepared.

On a non-alkali glass (1737; made by Corning; thickness 0.7 mm) substrate which is a transparent substrate, the black resin composition (BM1) -1 was applied by a spin coater so that the film thickness after curing was 0.7 μm. And semi-curing at 120 ° C. for 20 minutes to obtain a semi-cured film having a low optical density layer having an OD value of 1.1. Next, the black resin composition (BM2) -1 was applied by a spin coater so that the film thickness after curing was 0.7 μm, and prebaked at 90 ° C. for 10 minutes. A mask aligner PEM-6M (manufactured by Union Optics Co., Ltd.) is used for this coating film, and ultraviolet rays are exposed at an exposure amount of 100 mJ / cm ² through a photomask having a line width of 50 μm / 10 μm / 5 μm. did.

  Next, it developed with the 0.5 mass% aqueous solution of an aqueous solution of tetramethylammonium hydroxide, and then washed with pure water to obtain a patterned substrate. The obtained patterned substrate was kept in a hot air oven at 230 ° C. for 30 minutes and cured, whereby a low optical density layer having an OD value of 1.1 and a high optical density layer having an OD value of 3.5 were laminated. A laminated resin BM substrate 1 having a thickness of 1.4 μm and an OD value of 4.6 was obtained.

(Example 2)
A low optical density layer having an OD value of 1.1 and a high OD value of 3.1 were obtained in the same manner as in Example 1 except that the titanium nitride particles Bk-2 were used as the black pigment (B2) of the photosensitive black resin composition. A laminated resin BM substrate 2 having a film thickness of 1.4 μm and an OD value of 4.2 laminated with an optical density layer was obtained.

Example 3
A low optical density layer having an OD value of 1.1 and a high OD value of 3.1 were obtained in the same manner as in Example 1 except that the titanium nitride particles Bk-3 were used as the black pigment (B2) of the photosensitive black resin composition. A laminated resin BM substrate 3 having a film thickness of 1.4 μm and an OD value of 4.2 laminated with an optical density layer was obtained.

Example 4
In the same manner as in Example 1, except that titanium nitride particles Bk-4 were used as the black pigment (B2) of the photosensitive black resin composition and the film thickness of the high optical density layer was 0.8 μm. A laminated resin BM substrate 4 having a film thickness of 1.5 μm and an OD value of 4.1 obtained by laminating a low optical density layer of 1.1 and a high optical density layer of OD value 3.0 was obtained.

(Example 5)
In the same manner as in Example 1, except that titanium nitride particles Bk-4 were used as the black pigment (B2) of the photosensitive black resin composition and the high optical density layer was formed to have a thickness of 0.9 μm. A laminated resin BM substrate 5 having a film thickness of 1.6 μm and an OD value of 4.1 obtained by laminating a low optical density layer of 1.1 and a high optical density layer of OD value 3.0 was obtained.

(Comparative Example 1)
(B2) 175 g of high resistance carbon black Bk-6 as a black pigment, 171 g of a 35% by weight PMA solution of acrylic polymer (P-1), 38 g of Dispersic LPN-21116 as a polymer dispersant, and 616 g of PMA are charged in a tank. The mixture was stirred for 20 minutes with a homomixer to obtain a preliminary dispersion. Thereafter, the preliminary dispersion is supplied to an ultra apex mill equipped with a centrifugal separator filled with 0.05% φ zirconia beads 75%, and dispersed for 3 hours at a rotational speed of 8 m / s. / Resin (mass ratio) = 70/30 colorant dispersion DK-6 was obtained.

  PMA (39.67 g) and Adeka Arcles (registered trademark) NCI-831 (0.52 g) as a photopolymerization initiator were added and stirred until the solid content was dissolved.

  Furthermore, 10.14 g of a 35% by weight PMA solution of acrylic polymer (P-1), 4.15 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, and KBM5103 (Shin-Etsu) as an adhesion improver 0.60 g of Chemical Co., Ltd.) and 0.40 g of a PMA 10 mass% solution of a silicone surfactant BYK333 as a surfactant were added and stirred at room temperature for 1 hour to obtain a photosensitive resist. By adding 44.53 g of black pigment dispersion DK-6 to this photosensitive resist, black resin composition (BM2) -6 having a total solid content concentration of 20% and black pigment / resin (mass ratio) = 40/60 was obtained. Prepared.

  A film thickness in which a low optical density layer having an OD value of 1.1 and a high optical density layer having an OD value of 1.8 were laminated in the same manner as in Example 1 except that the black resin composition (BM2) -6 was used. A laminated resin BM substrate 6 having an 1.4 μm and an OD value of 2.9 was obtained.

(Comparative Example 2)
A low optical density layer having an OD value of 1.1 and a high optical density layer having an OD value of 1.8 are laminated in the same manner as in Comparative Example 1 except that the film thickness of the high optical density layer is 1.2 μm. A laminated resin BM substrate 7 having a film thickness of 1.9 μm and an OD value of 4.2 was obtained.

(Comparative Example 3)
0.65 g of Adeka Arcles (registered trademark) NCI-831 as a photopolymerization initiator was added to 31.44 g of PMA and stirred until the solid content was dissolved.

  Furthermore, 0.18 g of a 35% by weight PMA solution of acrylic polymer (P-1), 2.61 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, and KBM5103 (Shin-Etsu) as an adhesion improver 0.60 g of Chemical Co., Ltd.) and 0.40 g of a PMA 10 mass% solution of a silicone surfactant BYK333 as a surfactant were added and stirred at room temperature for 1 hour to obtain a photosensitive resist. A black resin composition (BM2) -8 having a total solid content of 20% and a pigment / resin (mass ratio) of 58/42 was prepared by adding 64.13 g of black pigment dispersion DK-6 to this photosensitive resist. did.

  A film thickness in which a low optical density layer having an OD value of 1.1 and a high optical density layer having an OD value of 3.1 were laminated in the same manner as in Example 1 except that the black resin composition (BM2) -8 was used. A laminated resin BM substrate 8 having 1.4 μm and an OD value of 4.2 was obtained.

Comparative Example 4
A low optical density layer having an OD value of 1.1 and a high optical density layer having an OD value of 3.5 were obtained in the same manner as in Example 1 except that e-2 was used as the photopolymerization initiator E for the photosensitive black resin composition. A laminated resin BM substrate 9 having a thickness of 1.4 μm and an OD value of 4.6 was obtained.

Comparative Example 5
A low optical density layer having an OD value of 1.1 and a high optical density layer having an OD value of 3.5 are the same as in Example 1 except that e-3 was used as the photopolymerization initiator E of the photosensitive black resin composition. And a laminated resin BM substrate 10 having a film thickness of 1.4 μm and an OD value of 4.6 was obtained.

Comparative Example 6
A low optical density layer having an OD value of 1.1 and a high optical density layer having an OD value of 3.5 are the same as in Example 1 except that e-4 was used as the photopolymerization initiator E of the photosensitive black resin composition. A laminated resin BM substrate 11 having a thickness of 1.4 μm and an OD value of 4.6 was obtained.

<Evaluation results>
Table 2 shows the compositions of the black resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 6 and the evaluation results of the prepared laminated resin BM substrates.

  From the results in Table 2, the laminated resin BM substrates produced in Examples 1 to 6 are all suitable for suppressing the influence of external light because of their low reflection chromaticity and reflectance, and have an OD value and volume. Since the resistance value is sufficiently high, it is clear that it is a high-performance laminated resin BM substrate. Furthermore, it can be seen that fine line patterns of 10 μm and 5 μm can be satisfactorily processed, and a high-definition pattern resin BM substrate with a narrow pixel pitch can be produced. Furthermore, it can be seen that a pattern can be formed even in h-line exposure.

  On the other hand, in Comparative Example 1, although it is possible to form a thin line pattern of 5 μm, there is a problem that the OD value is low. On the other hand, Comparative Examples 2 to 6 have a sufficient OD value, but there is a problem that a 5 μm fine line pattern cannot be formed.

(Production of color filter substrate)
A green pigment (PG36; 44 g), a yellow pigment (PY138; 19 g), polyamic acid A-2 (47 g) and γ-butyrolactone (890 g) are charged into a tank, and stirred for 1 hour with a homomixer (manufactured by Tokushu Kika). G pigment preliminary dispersion G1 was obtained. Thereafter, the preliminary dispersion G1 is supplied to Dynomill KDL (manufactured by Shinmaru Enterprises) filled with 85% of 0.40 mmφ zirconia beads (Traceram beads; manufactured by Toray Industries, Inc.), and dispersed for 3 hours at a rotational speed of 11 m / s. And a G pigment dispersion G1 having a solid content concentration of 7% by mass and a pigment / polymer (mass ratio) of 90/10 was obtained. G pigment dispersion G1 was diluted with polyamic acid A-2 and a solvent to obtain a green resin composition.

  A red pigment (PR254; 63 g) was charged instead of the green pigment and the yellow pigment, and an R pigment dispersion R1 having a solid content concentration of 7% by mass and a pigment / polymer (mass ratio) of 90/10 was obtained in the same manner. The R pigment dispersion R1 was diluted with polyamic acid A-2 and a solvent to obtain a red resin composition.

  A blue pigment (PR15: 6; 63 g) was charged instead of the green pigment and the yellow pigment, and a B pigment dispersion B1 having a solid content concentration of 7% by mass and a pigment / polymer (mass ratio) of 90/10 was obtained in the same manner. . The B pigment dispersion B1 was diluted with polyamic acid A-2 and a solvent to obtain a blue resin composition.

  On each of the laminated resin BM substrates prepared in Examples 1 to 6 and Comparative Examples 1 to 5, a red paste was applied after drying so as to have a film thickness of 2.0 μm and prebaked to obtain a polyimide precursor. A red colored film was formed. Using positive photoresist, red pixels were formed by the same means as described above, and heated to 290 ° C. to perform thermosetting. Similarly, a green paste was applied to form a green pixel, which was then heated to 290 ° C. and thermally cured. Similarly, a blue paste was applied to form a blue pixel, and heated to 290 ° C. to perform thermosetting.

(Production of liquid crystal display device)
Each obtained color filter substrate was washed with a neutral detergent, and then an alignment film made of polyimide resin was applied by a printing method and heated at 250 ° C. for 10 minutes using a hot plate. The film thickness after heating was 0.07 μm. Thereafter, each color filter substrate was rubbed, a sealant was applied by a dispensing method, and heated at 90 ° C. for 10 minutes using a hot plate. On the other hand, the substrate on which the TFT array was formed on the glass substrate was similarly washed with a neutral detergent, and then an alignment film was applied and heated. After that, a spherical spacer having a diameter of 5.5 μm is sprayed and superimposed on each color filter substrate coated with a sealant, and heated at 160 ° C. for 90 minutes while being pressurized in an oven to cure the sealant and to cure the cell. Obtained. Each cell was allowed to stand for 4 hours at a temperature of 120 ° C. and a pressure of 13.3 Pa. Subsequently, after standing for 0.5 hours in nitrogen, the liquid crystal compound was filled again under vacuum. The liquid crystal compound was filled by placing the cell in a chamber and reducing the pressure to 13.3 Pa at room temperature, then immersing the liquid crystal inlet in liquid crystal and returning to normal pressure using nitrogen. After filling the liquid crystal, the liquid crystal injection port was sealed with an ultraviolet curable resin. Next, a polarizing plate was attached to the outside of the two glass substrates of the cell to complete the cell. Further, the obtained cell was modularized to complete a liquid crystal display device.

  As a result of observing the obtained liquid crystal display device, in the liquid crystal display device provided with the laminated resin BM substrate obtained in Examples 1 to 6, since both the reflection chromaticity and the reflectance are low, display characteristics even when illuminated by external light Was good. Further, in Examples 1 to 4, since the laminated resin BM has a thin film thickness and a high light shielding property, a high-definition panel having a BM line width of 5 μm and a high display quality with high contrast was obtained. In Examples 5 and 6, since the linearity of the BM was poor, a slight decrease in contrast was observed due to light leakage at the BM edge. On the other hand, also in the liquid crystal display devices provided with the laminated resin BM substrates obtained in Comparative Examples 1 to 6, since the reflection chromaticity and the reflectance were both low, the display characteristics were good even when illuminated with external light. However, in Comparative Example 1, since the light shielding property of the laminated BM was insufficient, the contrast was extremely poor due to the light leakage of the backlight light. In Comparative Examples 2 to 5, in a high-definition panel having a BM line width of 5 μm, there was no light leakage at the frame portion, but the BM in the screen was missing, and the contrast was extremely poor. .

10: Transparent substrate 11: Laminated resin BM
21: Low optical density layer 22: High optical density layer

  The resin black matrix of the present invention can be used for a display device using a light source such as a cold cathode tube or LED, a color filter substrate for a liquid crystal display device, or a liquid crystal display device.

Claims (6)

A low optical density layer is formed by applying a black resin composition (BM1) containing (A1) a non-photosensitive alkali-soluble resin, (B1) a black pigment, and (C1) a solvent on a transparent substrate. A concentration layer forming step;
On the low optical density layer, (A2) photosensitive alkali-soluble resin, (B2) titanium nitride and / or titanium oxynitride, (C2) solvent, (D) photopolymerizable monomer and / or photopolymerizable oligomer. And (E) a high optical density layer forming step of forming a high optical density layer by applying a black resin composition (BM2) containing a photopolymerization initiator having a structure represented by the following general formula (I) When,
A method of manufacturing a laminated resin black matrix substrate, comprising: a batch patterning step of exposing and developing the laminated low optical density layer and the high optical density layer to form a laminated resin black matrix.

(Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or CN, an alkyl group, an aryl group, and an aryl group. the hydrogen atoms of the alkyl group is further ^{oR 21, COR 21, SR 21} , NR 22 R 23, -NCOR 22 -OCOR 23, CN, halogen ^atom, -CR 21 ^{= CR} 22 ^{R 23} or ^-CO-CR 21 = ^{CR 22} R ²³ may be substituted, and R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a carbon atom. represents an aryl group or a heterocyclic group having 2 to 20 carbon atoms having 7 to 30, ^{R 2 represents R 11} or ^{oR 11, R 11} is a 1 to 20 carbon atoms Represents a kill group, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, wherein the hydrogen atom of the alkyl group, aryl group and arylalkyl group may be further substituted with a halogen atom. Well, R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and R ¹ , R ³ , R ²¹ , R The methylene group of the alkylene part of the substituent represented by ²² and R ²³ may be interrupted 1 to 5 times by an unsaturated bond, an ether bond, a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond. The alkyl part of the substituent may have a branched side chain or may be a cyclic alkyl, and the alkyl terminal of the substituent is an unsaturated bond. Well, ^{R 3} is good .R ⁴ and ^{R 5} may form a ring together with the benzene ring adjacent each ^{independently} represent R ^{11, OR} 11, CN or a halogen atom, a and b is 0 to 3 independently.)
  When the black pigment (B2) is titanium nitride and the CuKα ray is used as an X-ray source, the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride particles is 42.5 ° or more. The method for producing a laminated resin black matrix substrate according to claim 1, wherein the angle is 8 ° or less.   The method for producing a laminated resin black matrix substrate according to claim 1 or 2, wherein the sum of the optical density of the low optical density layer and the optical density of the high optical density layer is 4.0 or more.   The method for producing a laminated resin black matrix substrate according to any one of claims 1 to 3, wherein the sum of the film thickness of the low optical density layer and the film thickness of the high optical density layer is 1.5 µm or less.   A color filter substrate in which red, green, or blue pixels are formed in the openings of the laminated resin black matrix substrate formed by the method according to claim 1.   A liquid crystal display device, wherein a liquid crystal compound is filled between the color filter substrate according to claim 5 and the counter substrate.

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