JP2012018384A - Black resin composition and black matrix - Google Patents

Abstract

The present invention relates to a black matrix excellent in light-shielding properties, electrical characteristics, and transmittance in the near-infrared region, particularly a black matrix used for a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, and the black matrix It aims at providing the black resin composition excellent in the fluidity | liquidity and stability for producing this.
The object is to provide a black resin composition comprising a light-shielding black pigment, a pigment dispersant, a resin, and a solvent, wherein the light-shielding black pigment has an average primary particle size of 50 nm or less. And a black resin composition characterized by being a perylene-based black pigment having a pigment particle aspect ratio of 1: 1 to 1: 2.
[Selection figure] None

Description

  The present invention relates to a black matrix used for manufacturing a color filter such as a liquid crystal display and a black resin composition for producing the same, and more particularly to a black matrix used for a driving substrate of a thin film transistor (TFT) type color liquid crystal display device. . The present invention also relates to a driving substrate of a thin film transistor (TFT) type color liquid crystal display device having the black matrix.

A lattice-like black pattern called a black matrix having a light-shielding property (hereinafter sometimes simply referred to as BM) is formed in the gaps between the red, green, and blue filter segments of the color filter. It is common.
The black matrix is required to have excellent light shielding properties in order to improve the image quality of the liquid crystal display. In particular, in order to cope with higher definition and higher brightness in recent years, a black matrix is formed on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device from a conventional method of forming a black matrix on a color filter substrate. The BOA (Black Matrix on Array) method for forming the above has been studied. This BOA method eliminates the need for a pasting process for alignment with the element, can greatly increase the pixel aperture ratio (aperture ratio), and can shorten the manufacturing process. Since the quality can be improved and the cost can be reduced, there are many advantages over the BM formed on the color filter substrate.

  However, when the BM is to be formed on the array substrate side, the BM itself is directly exposed to the driving electric field of the liquid crystal. Therefore, if the dielectric constant of the BM itself is high, a display defect of the liquid crystal display is caused. Moreover, since the mask alignment performed at the time of BM formation is performed using an infrared camera, a certain level of transmittance in the near infrared region is also required. Therefore, carbon black, which has been mainly used as a conventional BM material, not only exhibits a high dielectric constant and poor insulation, but also has a low transmittance in the near-infrared region, making alignment difficult. It is difficult to use for a liquid crystal panel of the type.

  As a method for solving such a problem, a method of combining carbon black and at least one organic pigment (see Patent Document 1), a method of providing light-shielding properties only by a combination of organic pigments without using carbon black (patent) Documents 2 and 3), a method using carbon black and a perylene black pigment as a black organic pigment (see Patent Documents 4 and 5) and the like have been disclosed. All of the characteristics and sufficient transmittance in the near infrared region for mask alignment work could not be satisfied.

JP-A-2005-215150 JP 2009-69822 A JP 2009-282251 A JP-A-6-289602 Japanese Patent Laid-Open No. 4-190362

  The present invention produces a black matrix excellent in light shielding properties, electrical characteristics, and near-infrared transmittance, particularly a black matrix used for a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, and the black matrix. An object of the present invention is to provide a black resin composition excellent in fluidity and stability.

  The subject is a black resin composition comprising a light-shielding black pigment, a pigment dispersant, a resin, and a solvent, wherein the light-shielding black pigment has an average primary particle size of 50 nm or less and pigment particles. This is solved by a black resin composition characterized by being a perylene-based black pigment having an aspect ratio of 1: 1 to 1: 2.

  The present invention also relates to the black resin composition, wherein the average primary particle diameter of the perylene-based black pigment is 20 to 45 nm.

  The present invention also relates to the black resin composition, wherein the pigment dispersant is a pigment derivative having a base skeleton of an organic pigment and a basic substituent.

  The present invention also relates to the black resin composition, wherein the base skeleton of the organic pigment is either a dioxazine pigment or a diketopyrrolopyrrole pigment.

  The present invention also relates to the black resin composition, wherein the pigment dispersant further contains a resin-type dispersant.

  The present invention also relates to the black resin composition, further comprising an ethylenically unsaturated compound and a photopolymerization initiator.

  The present invention also relates to a black matrix formed from the black resin composition.

  The present invention also relates to the black matrix, wherein the relative dielectric constant at a dry film thickness of 1.0 μm is 4.5 or less.

  The present invention also relates to the black matrix, wherein the transmittance at a wavelength of 1000 nm at a dry film thickness of 1.0 μm is 60% or more and less than 99%.

  The present invention also relates to the black matrix, wherein an optical density at a dry film thickness of 1.0 μm is 1.30 or more.

  The present invention also relates to a driving substrate of a thin film transistor (TFT) type color liquid crystal display device comprising the black matrix.

  The black matrix formed using the black resin composition of the present invention is excellent in light-shielding property, so that it has excellent display contrast of a color liquid crystal display device, and further has low dielectric constant characteristics, so that liquid crystal alignment disorder and TFT substrate Thin film transistor (TFT) method is possible because it is less likely to cause defects due to the electrical characteristics of the black matrix, such as conduction between electrodes formed on it, and has excellent near-infrared transmittance. It is also suitable for driving substrates for color liquid crystal display devices.

  The black resin composition of the present invention is a black resin composition comprising a light-shielding black pigment, a pigment dispersant, a resin, and a solvent, and the light-shielding black pigment has an average primary particle size of 50 nm or less, Preferably, it is a perylene black pigment having a pigment particle aspect ratio of 1: 1 to 1: 2 and preferably 20 to 45 nm.

<Light-shielding black pigment>
The light-shielding black pigment in the present invention is a perylene black pigment which is a crystal particle having an average primary particle diameter of 50 nm or less and an aspect ratio of 1: 1 to 1: 2.
The average primary particle size is preferably 5 to 50 nm, more preferably 20 to 45 nm. When the average primary particle size is less than 5 nm, pigment dispersion becomes difficult. Moreover, since an average primary particle diameter exceeds 50 nm, since light-shielding property falls, it is unpreferable. That is, when the average primary particle diameter is increased, the packing of the particles is sparse, and the concealability is reduced due to the formation of gaps. On the other hand, by suppressing the average primary particle diameter to 50 nm or less, the packing of the particles becomes dense and the light shielding property is improved. Furthermore, even in the case of a crystal such as a needle shape having an aspect ratio exceeding the range of 1: 1 to 1: 2, it is not preferable because the packing of the particles becomes sparse and the concealability is reduced due to the formation of gaps. . Preferably, in the case of presenting spherical crystals having an aspect ratio in the range of 1: 1 to 1: 1.5, the distance between the crystals is made more uniform, so that gaps are less likely to be formed, and concealment is achieved. Rise.

  The content of the perylene-based black pigment in the black resin composition is preferably 20 to 70% by weight and more preferably 30 to 60% by weight in 100% by weight of the total solid content of the black resin composition. . When the content of the perylene black pigment is less than 20% by weight, it is difficult to obtain sufficient light shielding properties, and when it is more than 70% by weight, it is difficult to obtain dispersion stability.

<Pigment dispersant>
The black resin composition of the present invention contains a pigment dispersant such as a pigment derivative, a resin-type dispersant, and a surfactant. The pigment dispersant is excellent in dispersing the perylene-based black pigment, and has a large effect of preventing re-aggregation of the perylene-based black pigment after dispersion. In particular, when a pigment derivative is used, it is preferable for improving electric characteristics. Further, by including a resin-type dispersant, it is preferable for further improvement of electric characteristics and compatibility between fluidity and stability. It is.

(Dye derivative)
Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine.
Its structure is a compound represented by the following general formula (1).
P-Ln General formula (1)
[However,
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group n: an integer of 1 to 4 is there. ]
Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; Indoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.
In the present invention, a pigment derivative whose base skeleton is an organic pigment is preferable, and among them, a dioxazine pigment and a diketopyrrolopyrrole pigment can be preferably used from the viewpoint of low dielectric loss tangent.

In the general formula (1), a basic derivative in which L is a basic substituent can be preferably used.
Among them, the pigment derivative having a basic skeleton of organic pigment and a basic substituent imparts affinity with perylene-based black pigment, homogenizes the molecular arrangement in the black resin composition, and reduces charge bias. This is preferable because it contributes to improvement of electrical characteristics.
Preferably, L is a substituent selected from the group represented by the general formulas (2), (3), and (4).

General formula (2):

General formula (3):

General formula (4):

[However, in the general formulas (2) to (4),
X _{is, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁵⁸ —Z—NR ⁵⁹ —, or a direct bond;
R ⁵⁸ and R ⁵⁹ are each independently a hydrogen bond, an alkyl group having 1 to 36 carbon atoms which may have a substituent, an alkenyl group having 2 to 36 carbon atoms which may have a substituent, or A phenyl group which may have a substituent,
Z is an alkylene group which may have a substituent, or an arylene group which may have a substituent,
R ⁵⁰ and R ⁵¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, or R. ⁵⁰ and R ⁵¹ together are a heterocyclic ring which may further have a substituent containing a further nitrogen, oxygen or sulfur atom,
R ⁵² , R ⁵³ , R ⁵⁴ , and R ⁵⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 to carbon atoms that may have a substituent. 20 alkenyl group, an arylene group having 6 to 20 carbon atoms which may have a substituent,
R ⁵⁶ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or an alkenyl group having 2 to 20 carbon atoms that may have a substituent,
R ⁵⁷ is a substituent represented by the general formula (2) or a substituent represented by the general formula (3);
Q is a hydroxyl group, an alkoxyl group, a substituent represented by the general formula (2), or a substituent represented by the general formula (3). ]

  Examples of the amine component used for forming the substituents represented by the general formulas (2) to (4) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethyl. Propylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine , Dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadeci Amine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylamino Ethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N , N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopen Ruamine, N, N-methyl-laurylaminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonipecotate, Isonipecotic acid Ethyl, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, -Aminopropyl-4-pipecholine, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine, etc. Can be mentioned.

  The pigment derivative, anthraquinone derivative, and acridone derivative having a basic substituent of the present invention can be synthesized by various synthetic routes. For example, after introducing a substituent represented by formulas (5) to (8) into an organic dye, anthraquinone, or acridone, it reacts with the above substituent to form a substituent represented by formulas (2) to (4) For example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5- It can be obtained by reacting triazin-2-ylamino] aniline or the like.

Equation (5): _-SO 2 Cl
Formula (6): -COCl
Equation _{(7): -CH 2 NHCOCH 2} Cl
Equation (8): _-CH 2 Cl

  During the reaction of the substituents of formulas (5) to (8) and the above amine component, some of the substituents of formulas (5) to (8) are hydrolyzed and chlorine is substituted with hydroxyl groups. It may be. In that case, the formula (5) and the formula (6) respectively become a sulfonic acid group and a carboxylic acid group, but both may be a free acid, or a 1-3 valent metal or the above monoamine. Or a salt thereof.

  Further, when the organic dye is an azo dye, the substituent represented by the general formulas (2) to (4) is introduced into the diazo component or the coupling component in advance, and then the coupling reaction is performed, thereby performing the azo pigment. Derivatives can also be produced.

  The blending amount of the dye derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, most preferably 3 parts by weight or more with respect to 100 parts by weight of the perylene-based black pigment from the viewpoint of improving dispersibility. . Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by weight or less, and most preferably 35 parts by weight or less with respect to 100 parts by weight of the perylene black pigment.

(Resin type dispersant)
The resin type dispersant has a pigment affinity part having a property of adsorbing to a perylene black pigment, and a part compatible with the perylene black pigment carrier. In the perylene-based black pigment carrier. In the same way as the above-mentioned dye derivatives, the resin-type dispersant imparts affinity with perylene black pigments and dye derivatives, makes the molecular arrangement in the black resin composition more uniform, and further reduces the electric charge bias. It is preferable because it contributes to improvement of characteristics.

  In particular, it is preferable to use a perylene-based black pigment, a pigment derivative having a basic substituent, and an acidic resin dispersant in order to exhibit excellent effects such as compatibility between fluidity and electrical characteristics. This is because the charge is neutralized by the interaction between the basic substituents of the acidic resin dispersant and the acidic derivative. As a result, the local charge bias is suppressed and the electrical characteristics are improved.

  Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto. The acid value of the resin-type dispersant is preferably 200 mgKOH / g or less, more preferably 40 to 200 mgKOH / g, and most preferably 100 to 200 mgKOH / g, from the viewpoints of improving electrical characteristics and dispersion stability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

(Surfactant)
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  The addition amount of the resin-type dispersant and the surfactant is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the perylene-based black pigment. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<Resin>
The resin disperses the light-shielding black pigment, and examples thereof include a thermoplastic resin and a thermosetting resin.
The resin preferably has a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated compound. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.
In particular, the use of an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain is preferable because the stability of the resist material is improved.

  The weight average molecular weight (Mw) of the resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000, in order to disperse the light-shielding black pigment preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When used as a photosensitive black resin composition to be described later, from the viewpoints of dispersibility, developability, and heat resistance of the light-shielding black pigment, a carboxyl group and a pigment that function as a pigment adsorbing group and an alkali-soluble group during development A resin having an acid value of 20 to 300 mgKOH / g is important for the dispersibility, developability, and heat resistance of pigments and salt-forming compounds, because the balance between aliphatic groups and aromatic groups acting as affinity groups for the carrier and the solvent is important. Is preferably used. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The resin is preferably used in an amount of 30 parts by weight or more with respect to the total weight of 100 parts by weight of the perylene-based black pigment because the film formability and various resistances are good, and the light-shielding black pigment concentration is high and good. Since color characteristics can be expressed, it is preferably used in an amount of 500 parts by weight or less.

(Thermoplastic resin)
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. Polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

  Examples of the vinyl-based alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated compound include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).

[Method (a)]
As the method (a), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated compound having an epoxy group and one or more other ethylenically unsaturated compounds is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

  Examples of the unsaturated ethylenically unsaturated compound having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4 epoxybutyl (meth). An acrylate and 3,4 epoxy cyclohexyl (meth) acrylate are mentioned, These may be used independently or may use 2 or more types together. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to method (a), for example, a copolymer obtained by copolymerizing an unsaturated ethylenically unsaturated compound having a carboxyl group and one or more other ethylenically unsaturated compounds. There is a method of introducing an unsaturated ethylenic double bond and a carboxyl group by adding an unsaturated ethylenically unsaturated compound having an epoxy group to a part of the side chain carboxyl group of the coalescence.

[Method (b)]
As the method (b), an unsaturated ethylenically unsaturated compound having a hydroxyl group is used, an ethylenically unsaturated compound of an unsaturated monobasic acid having another carboxyl group, or another ethylenically unsaturated compound There is a method in which an isocyanate group of an unsaturated ethylenically unsaturated compound having an isocyanate group is reacted with a side chain hydroxyl group of a copolymer obtained by copolymerization of.

  Examples of unsaturated ethylenically unsaturated compounds having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate. Hydroxyalkyl (meth) acrylates such as glycerol (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, which may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of unsaturated ethylenically unsaturated compounds having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. Two or more types can also be used together without doing.

(Thermosetting resin)
Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

<Solvent>
In the black resin composition of the present invention, a perylene-based black pigment is sufficiently dispersed and permeated in a pigment carrier, and applied to a glass substrate, a TFT substrate or the like so that the dry film thickness is 0.2 to 10 μm. In order to facilitate this, a solvent is included.
Examples of the solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2 -Heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl- 1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m- Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate , O-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene Glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl Ether, ethylene glycol monohexyl ether, ethylene glycol Methyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, Cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether Dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene Glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, Acetate Amyl, isobutyl acetate, propyl acetate, and a dibasic acid ester and the like.

Among them, since the dispersion of the light-shielding black pigment of the present invention is good, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, benzyl alcohol It is preferable to use aromatic alcohols such as cyclohexanone and ketones such as cyclohexanone. A solvent can be used individually by 1 type or in mixture of 2 or more types.
Further, the solvent is preferably used in an amount of 800 to 4000 parts by weight with respect to 100 parts by weight of the perylene-based black pigment because the black resin composition can be adjusted to an appropriate viscosity to form a desired uniform film thickness. .

  The black resin composition of the present invention can be used as a photosensitive black resin composition by further adding an ethylenically unsaturated compound and a photopolymerization initiator.

<Ethylenically unsaturated compound>
The ethylenically unsaturated compound is a compound having one or more ethylenically unsaturated double bonds, and monomers and oligomers can be used. Examples of the monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tris. (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned. Examples of the oligomer include epoxy (meth) acrylate, urethane (meth) acrylate, and ester (meth) acrylate.
An ethylenically unsaturated compound may be used individually by 1 type, or may mix and use 2 or more types.
The content of the ethylenically unsaturated compound can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, per 100 parts by weight of the perylene-based black pigment in the black resin composition.

<Photopolymerization initiator>
The black composition contains a photopolymerization initiator when the composition is cured by ultraviolet irradiation and a black matrix is formed by photolithography. Examples of the photopolymerization initiator include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2- Oxime ester photopolymerization initiators such as methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane 1-one acetophenone photopolymerization initiator, benzoin, benzoin methyl ether, benzoin ester Benzoin photopolymerization initiators such as ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl Benzophenone photopolymerization initiators such as sulfide, thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4 , 6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-tri Gin, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis ( Trichloromethyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, etc. Examples thereof include a polymerization initiator, a carbazole photopolymerization initiator, and an imidazole photopolymerization initiator. The said photoinitiator is used individually by 1 type or in mixture of 2 or more types.
The photopolymerization initiator can be used in an amount of preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight with respect to 100 parts by weight of the perylene-based black pigment.

Moreover, you may make a photosensitive black resin composition contain a sensitizer. Examples of the sensitizer include α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethyliso Examples include phthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, and the like. The above sensitizers are used alone or in combination of two or more.
The sensitizer can be used in an amount of preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

  The photosensitive black resin composition may contain a chain transfer agent, a surfactant, a silane coupling agent, other additives, etc. for the purpose of improving coating properties, improving sensitivity, and improving adhesion. good.

<Manufacture of black resin composition>
The black resin composition of the present invention is a three-roll mill, two-roll mill, kneader, horizontal type by mixing a light-shielding black pigment, a pigment dispersant, a resin, and, if necessary, a solvent and an additive. By dispersing with a sand mill, a vertical sand mill, an annular bead mill, an attritor or the like, the pigment can be finely dispersed in the resin solvent liquid using various dispersing means (pigment dispersion).

  Moreover, when using as a photosensitive black resin composition, it can prepare as a solvent image development type or an alkali image development type black resin composition. The solvent development type or alkali development type black resin composition includes the pigment dispersion, the ethylenically unsaturated compound, the photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. Can be mixed and adjusted. The solvent development type or alkali development type black resin composition generally comprises a resin that is a thermoplastic resin, a thermosetting resin, or a photosensitive resin, an ethylenically unsaturated compound, a photopolymerization initiator, a solvent, A pigment is dispersed in a composition containing.

  The photopolymerization initiator may be added at the stage of preparing the black resin composition, or may be added later to the prepared black resin composition.

  The black resin composition is prepared by means of centrifugal separation, sintering filter, membrane filter, or the like. The coarse particles are 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust. Removal is preferably performed.

<Black matrix>
The black matrix of the present invention is formed by photolithography after coating the black resin composition of the present invention on a transparent substrate such as glass and a thin film transistor (TFT) substrate.

  By forming a color filter segment and / or a black matrix on a thin film transistor (TFT) substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  The coating thickness of the black matrix is preferably in the range of 0.2 to 10.0 μm, more preferably 0.2 to 5.0 μm, as the thickness after drying. Furthermore, it is more preferable that the thickness is in the range of 0.5 to 2.5 μm, which makes it easy to balance coating properties and light shielding properties. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  Formation of the black matrix by photolithography is performed by the following method. That is, the photosensitive black resin composition prepared as a solvent development type or alkali development type colored black resin composition is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, etc. Is applied so as to be 0.2 to 10.0 μm. If necessary, the dried film is subjected to active energy ray exposure through a mask having a predetermined pattern provided in contact or non-contact with the film. Thereafter, the black matrix having a desired pattern can be formed by immersing in a solvent or an alkaline developer or spraying the developer by spraying or the like to remove the uncured portion. Furthermore, in order to accelerate | stimulate superposition | polymerization of the photosensitive black resin composition, it can also heat as needed. According to the photolithography method, a black matrix with higher accuracy than the printing method can be formed.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.

  In order to increase exposure sensitivity to active energy rays, a film that prevents polymerization inhibition by oxygen by applying and drying a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin after coating and drying the photosensitive black composition. After forming, active energy rays can also be irradiated from the composition coated surface side.

  As the active energy ray, an electron beam, ultraviolet rays, or visible light of 400 to 500 nm can be used. A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source irradiated from the composition application surface side. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) of ultraviolet light and visible light of 400 to 500 nm. Specifically, since it is a point light source and the luminance is stable, an ultrahigh pressure mercury lamp or a xenon mercury lamp is often used. The active energy dose irradiated from the composition coated surface side can be set in a timely manner within a range of 5 to 1000 mJ, but is preferably within a range of 20 to 300 mJ that can be easily managed in the process.

  When the light shielding layer is formed on the TFT substrate, the black resin composition of the present invention is first formed on the surface of the TFT substrate or on the surface of the substrate on which a passivation film such as a silicon nitride film is formed on the surface of the driving substrate. After applying the product, pre-baking or drying under reduced pressure is performed to evaporate the solvent, and then the coating film is exposed through a photomask and then developed using an alkali developer to remove the unexposed portion of the coating film. The light shielding layer is formed so as to partition the portion where the pixel is formed by dissolving and removing, and then post-baking.

  Further, from the viewpoint of insulation, it is preferable that the relative dielectric constant per dry film thickness of 1.0 μm of the black matrix is 4.5 or less.

  Furthermore, in order to perform alignment using infrared rays, the transmittance at a wavelength of 1000 nm is preferably 60% or more and less than 99% in a black matrix having a dry film thickness of 1.0 μm.

  Further, from the viewpoint of high light shielding properties, the optical density is preferably 1.30 or more in a black matrix having a dry film thickness of 1.0 μm. The higher the optical density, the better. However, when the active energy ray is ultraviolet light or visible light, it is difficult to obtain a cured coating film.

<Driving board for thin film transistor (TFT) type color liquid crystal display>
Thin film transistor (TFT) type color liquid crystal display device drive substrate is formed on the thin film transistor (TFT) substrate by spin coating, slit coating, roll coating, etc., for example, red, blue and green color filter segments. Then, it is produced by forming the black matrix of the present invention.
Also, a black matrix can be formed on the thin film transistor (TFT) substrate, and a color filter segment can be formed thereon.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited by this. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  The average primary particle diameter of pigment and the aspect ratio of pigment particles were measured by a method of directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size. Further, as described above, when measuring the short axis diameter and the long axis diameter of the primary particles of each pigment, the ratio of the average value of the short axis diameter and the long axis diameter is vertical and horizontal when the short axis diameter is 1. The ratio was determined. The electron microscope was a transmission type (TEM).

  Moreover, the polymerization average molecular weight (Mw) of the acrylic resin was measured by using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw) in terms of polystyrene.

  First, preparation of acrylic resin solutions used in Examples and Comparative Examples, production methods and physical properties of perylene black pigments, and structural formulas of pigment derivatives will be described.

[Preparation of acrylic resin solution]
A reaction vessel is charged with 800.0 parts of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 60.0 parts of methacrylic acid, 65.0 parts of butyl methacrylate, and 65.0 of methyl methacrylate. A mixture of 60.0 parts of styrene, 60.0 parts of styrene, and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour, and the mixture was further reacted at 100 ° C. for 3 hours, and then 2.0 parts of azobisisobutyronitrile. Was dissolved in 50.0 parts of cyclohexanone, and the reaction was further continued at 100 ° C. for 1 hour to synthesize a resin solution. After cooling to room temperature, sample approximately 2.0 g of the resin solution, heat and dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20%. Thus, an acrylic resin solution was prepared. The weight average molecular weight of the acrylic resin was 40000.

[Physical properties of perylene black pigment]

Perylene black pigment 1
"Lumogen Black FK4280" manufactured by BASF
Perylene black pigment 2
Perylene black pigment C.I. I. Pigment Black 31 ("Paliogen Black S0084" manufactured by BASF)
Perylene black pigment 3
Perylene black pigment C.I. I. Pigment Black 32 (manufactured by BASF “P-periperylene-based black pigment 4
"Lumogen Black FK4281" made by perylene-based black pigment BASF

Perylene black pigment 5
Perylene black pigment C.I. I. 500 parts of Pigment Black 31 (“Paligen Black S0084” manufactured by BASF)), 250 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 5 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a perylene-based black pigment 5 was obtained.

Perylene black pigment 6
500 parts of perylene-based black pigment ("Lumogen Black FK4281" manufactured by BASF), 250 parts of sodium chloride, and 250 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 5 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a perylene-based black pigment 6 was obtained.

Perylene black pigment 7
500 parts of perylene-based black pigment (“Lumogen Black FK4281” manufactured by BASF), 2500 parts of sodium chloride, and 250 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 40 ° C. for 12 hours. did. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a perylene-based black pigment 7 was obtained.

Perylene black pigment 8
Perylene black pigment C.I. I. Pigment Black 32 (“Paligen Black L0086” manufactured by BASF) was charged in 500 parts, 2500 parts of sodium chloride, and 250 parts of diethylene glycol in a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 12 hours. . Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. Thus, a perylene black pigment 8 shown in Table 1 was obtained.

[Structural formula of pigment derivative]

[Example 1]
(Black pigment dispersion 1)
After uniformly stirring and mixing a mixture having the following composition, it was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm Filtration through a filter produced a black resin composition (black pigment dispersion 1).

Perylene-based black pigment 7: 6.5 parts Pigment derivative 1: 0.7 part Resin type dispersant 1: 1.4 parts “BYK-110” manufactured by Big Chemie Japan (acid value 53 mgKOH / g)
Acrylic resin solution: 33.6 parts Solvent; cyclohexanone: 57.8 parts

[Examples 2 to 13, Comparative Examples 1, 2, 4 to 9]
(Black pigment dispersion 2-13, 17-22)
Except having changed into the composition shown in Table 3, and the compounding quantity, it carried out similarly to Example 1 (black pigment dispersion 1), and produced black pigment dispersion 2-13, 17-22.

Abbreviations and compounds in Table 3 are shown below.
Pigment
R / B / Y pigment mixture 1: PR177 / PB15: 6 / PY139 = 50/40/10 mixed to make black
R / B / Y pigment mixture color 2: PR179 / PB15: 6 / PY185 = 50/40/10 mixed to give a black pigment derivative derivative 1-4: pigment derivative 1-4 shown in Table 4 respectively
Resin Type Dispersant Resin Type Dispersant 1: Acid Resin Type Dispersant “BYK-110”
Product made by Big Chemie Japan (acid value 53mgKOH / g)
Resin-type dispersant 2: acidic resin-type dispersant “BYK-111”
Made by Big Chemie Japan (acid value 129mgKOH / g)
Resin Type Dispersant 3: Acid Resin Type Dispersant “BYK-171”
Made by Big Chemie Japan (acid value 13 mgKOH / g)
Resin-type dispersant 4: Basic resin-type dispersant “BYK-6919” manufactured by Big Chemie Japan
Solvent; cyclohexanone

[Comparative Example 3]
(Black pigment dispersion 16)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The black pigment dispersion 15 was produced by filtration using a filter.
Carbon black (Mitsubishi Chemical Co., Ltd. # 45): 6.5 parts Pigment derivative 1: 0.7 parts Acrylic resin solution: 33.6 parts Resin-type dispersant 1: 1.2 parts “BYK-110” Big Chemie Made by Japan (acid value 53mgKOH / g)
Solvent; cyclohexanone: 57.8 parts

[Evaluation of viscosity of black pigment dispersion and rate of change over time]
The viscosity of the black pigment dispersion was measured at a rotation speed of 20 rpm using an E-type viscometer (TVE-20L type viscometer (manufactured by Toki Sangyo Co., Ltd.)) at 25 ° C. on the day of pigment dispersion adjustment. did.
And about the black pigment dispersion which left still at 40 degreeC for 7 days counting from the day of black pigment dispersion adjustment, after returning sample temperature to 25 degreeC, according to the said viscosity measurement method, a time-dependent viscosity is measured, The following formula From this, the rate of change with time was determined.
Rate of change with time (%) = (viscosity with time) / (initial viscosity) × 100
The rate of change with time was evaluated in three stages according to the following criteria.
The results are shown in Table 4.
○: Change rate with time is less than 110%
Δ: Change rate with time 110% or more, less than 140% ×: Change rate with time 140% or more

[Optical density]
The black pigment dispersion was applied to a 100 mm × 100 mm glass substrate by a spin coating method, vacuum-dried, and then heated at 230 ° C. for 20 minutes. In this way, a black pigment dispersion coated substrate having a thickness of 1.0 μm was prepared, and the optical density (OD) of the substrate was measured with a Macbeth densitometer (GRETAG D200-II). The optical density (OD) was determined.
The results are shown in Table 4.

[Transmissivity]
The black pigment dispersion was applied to a 100 mm × 100 mm glass substrate by a spin coating method, and then a coating film having a dry film thickness of 1.0 μm was formed through a baking process at 230 ° C. for 20 minutes. The transmittance of the obtained black pigment dispersion coated substrate was measured with a spectrophotometer (HITACHI U-3900H) to determine the transmittance, and was evaluated in three stages according to the following criteria.
The results are shown in Table 4.
○: Transmittance (wavelength 1000 nm) 80% or more
Δ: transmittance (wavelength 1000 nm) 60% or more and less than 80% ×: transmittance (wavelength 1000 nm) less than 60%

As the light-shielding black pigment that is a feature of the present invention, a perylene-based black pigment having an average primary particle diameter of 50 nm or less and an aspect ratio of pigment particles having a specific value, a pigment dispersant, a resin, and a solvent Each of the black pigment dispersions composed of the above had good fluidity and stability, had a high OD value, showed good light shielding properties, and had excellent transmittance.
In addition, by using both the pigment derivative and the resin-type dispersant, good temporal stability was exhibited, and particularly when the acidic resin-type dispersant was used (Examples 1 to 6, 11, 12). .

[Example 14]
(Resist material 1)
Next, the mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a photosensitive black resin composition (resist material 1).
Black pigment dispersion 1: 48.0 parts Acrylic resin solution: 17.2 parts Photopolymerization initiator: 0.4 parts
("Irgacure OXE-02" manufactured by Ciba Japan)
Ethylenically unsaturated ethylenically unsaturated compound: 2.9 parts
("Aronix M-402" manufactured by Toagosei Co., Ltd.)
Surface conditioner: 1.0 part
(A solution obtained by diluting 2 parts “BYK-330” (non-volatile content 50% by weight) manufactured by Big Chemie Japan with 98 parts of propylene glycol monomethyl ether acetate)
Solvent; cyclohexanone: 30.5 parts

[Examples 15 to 26, Comparative Examples 10 to 18]
(Resist materials 2-22)
Resist materials 2 to 22 were produced in the same manner as in Example 14 (resist material 1) except that the black pigment dispersion shown in Table 5 was used.

[Optical density]
The resist material was applied to a 100 mm × 100 mm glass substrate by a spin coating method and dried in vacuum. Thereafter, ultraviolet rays were exposed to 100 mJ / cm ² using an ultra high pressure mercury lamp. Next, after spray-developing the unexposed area using an aqueous sodium carbonate solution, the unexposed area is removed by washing with ion-exchanged water and heated at 230 ° C. for 20 minutes to produce a resist material coated substrate having a film thickness of 1.0 μm. did. The optical density (OD) of the substrate thus obtained was measured with a Macbeth densitometer (GRETAG D200-II), and the optical density (OD) at a film thickness of 1.0 μm was determined.
The results are shown in Table 5.

[Transmissivity]
The resist material was coated on a 100 mm × 100 mm glass substrate by a spin coating method, and then a coating film having a dry film thickness of 1.0 μm was formed through a baking process at 230 ° C. for 20 minutes. The transmittance of the resulting resist material coated substrate was measured with a spectrophotometer (HITACHI U-3900H) to determine the transmittance, and was evaluated in three stages according to the following criteria.
The results are shown in Table 5.
○: Transmittance (wavelength 1000 nm) 80% or more
Δ: transmittance (wavelength 1000 nm) 60% or more and less than 80% ×: transmittance (wavelength 1000 nm) less than 60%

[Relative permittivity, tan δ (dielectric loss tangent)]
Using a spin coater on a 1.1 mm-thick glass substrate on which a photosensitive black resin composition was vapor-deposited aluminum for electrodes of 100 mm × 100 mm, the number of revolutions became 1.0 μm after the following heating step. Was applied to obtain a coated substrate. Next, after drying under reduced pressure, ultraviolet exposure was performed using an ultrahigh pressure mercury lamp with an integrated light amount of 100 mJ / cm ² and an illuminance of 25 mW / cm ² . The coated substrate was heated at 230 ° C. for 20 minutes and allowed to cool, and then a 3.464E-4m ² area electrode aluminum was deposited on the resulting cured coating film, and a sample was prepared by sandwiching the cured coating film with aluminum electrodes. did. The relative dielectric constant and tan δ of the obtained sample were measured at an applied voltage of 100 mV using an impedance analyzer (“1260 type” impedance analyzer manufactured by Solartron). The relative dielectric constant was evaluated in three stages according to the following criteria.
○: Relative dielectric constant less than 3.5
Δ: relative dielectric constant 3.5 or more and 4.5 or less x: tan δ exceeding the relative dielectric constant 4.5 was evaluated in three stages according to the following criteria.
○: Less than tan δ 0.1
Δ: tan δ 0.1 or more and less than 0.2 ×: tan δ 0.2 or more The results are shown in Table 5.

  As shown in Table 5, a perylene black pigment having crystal particles having an average primary particle size of 50 nm or less and an aspect ratio of 1: 1 to 1: 2 as a light-shielding black pigment, a pigment dispersant, a resin, The resist material of the present invention using a solvent had high optical density, excellent light shielding properties, low dielectric constant, and excellent transmittance in the near infrared region. On the other hand, when the perylene pigment did not satisfy one of the specific average particle diameter and aspect ratio, not only the optical density was low and the light shielding property was poor, but also the electrical characteristics were poor.

  Among them, resist materials using a pigment derivative having a basic skeleton of an organic pigment and a basic substituent as a pigment dispersant have shown better results in electrical properties, and the base skeleton of the organic pigment is dioxazine or diketopyrrolopyrrole. Some resist materials also improved tan δ.

  Furthermore, the resist material using both the pigment derivative and the acidic resin type dispersant having an acid value of 100 to 200 mgKOH / g has further improved tan δ, low initial viscosity, and good stability.

  Moreover, in Comparative Examples 10 and 11 (resist materials 12 and 13) in which a black resin composition is mixed with an organic pigment as a light-shielding black pigment, the relative dielectric constant and transmittance are practical levels, but the optical density is low, In Comparative Example 12 (resist material 14) using carbon black, although the optical density was excellent, the relative dielectric constant and the transmittance in the near infrared region were very poor.

  In Comparative Examples 13 to 17 (resist materials 15 to 19) in which the perylene pigment does not satisfy any one of the specific average particle diameter and aspect ratio, not only the optical density is low and the light shielding property is poor, but also the The characteristics were also bad.

  As described above, none of the comparative examples was able to satisfy all of the relative permittivity, the transmittance, and the light shielding property.

<Production of color liquid crystal display device>
The color liquid crystal display device can be produced by a conventionally known method, for example, a method disclosed in JP-A-2000-162643.

A thin film transistor (TFT) type color liquid crystal display device driving substrate was prepared using a black matrix formed from the black resin composition of the present invention.
First, a TFT and a transparent ITO electrode layer were patterned on the surface of a (first) glass substrate, and an RGB color filter was formed thereon. An ITO film serving as a pixel electrode was formed on the color filter, etched into a predetermined pattern, and then a black matrix was formed between the RGB pixels to produce an array substrate.
On the other hand, a transparent ITO electrode layer was patterned on the surface of another (second) glass substrate, a polyimide alignment layer was formed thereon, and a counter substrate was produced.
The array substrate and the counter substrate prepared in this way are arranged facing each other so that the electrode layers face each other, and are aligned using spacer beads while keeping the distance between the two substrates constant, and an opening for injecting a liquid crystal composition The periphery was sealed with a sealant so as to leave a part. After injecting the liquid crystal composition from the opening, the opening was sealed. A liquid crystal display device thus produced was combined with a three-wavelength CCFL light source of a backlight unit to produce a color display device.

  As a result, all of the color display devices having a driving substrate of a thin film transistor (TFT) type color liquid crystal display device having a black matrix formed using the black resin composition of the present invention are excellent in light shielding properties. The color liquid crystal display device has excellent display contrast and low dielectric constant characteristics, so there is little adverse effect on electrical characteristics such as liquid crystal alignment disorder and excellent transmittance in the near-infrared region. It was possible.

Claims (11)

  A black resin composition comprising a light-shielding black pigment, a pigment dispersant, a resin, and a solvent, wherein the light-shielding black pigment has an average primary particle diameter of 50 nm or less and an aspect ratio of the pigment particles. A black resin composition, which is a perylene-based black pigment having a ratio of 1: 1 to 1: 2.   2. The black resin composition according to claim 1, wherein the average primary particle diameter of the perylene-based black pigment is 20 to 45 nm.   The black resin composition according to claim 1 or 2, wherein the pigment dispersant is a pigment derivative having a base skeleton of an organic pigment and a basic substituent.   4. The black resin composition according to claim 3, wherein the base skeleton of the organic pigment is either a dioxazine pigment or a diketopyrrolopyrrole pigment.   The black resin composition according to claim 3 or 4, wherein the pigment dispersant further contains a resin-type dispersant.   The black resin composition according to any one of claims 1 to 5, further comprising an ethylenically unsaturated compound and a photopolymerization initiator.   The black matrix formed from the black resin composition of any one of Claim 1 thru | or 6.   8. The black matrix according to claim 7, wherein the relative dielectric constant at a dry film thickness of 1.0 [mu] m is 4.5 or less.   9. The black matrix according to claim 7, wherein the transmittance at a wavelength of 1000 nm at a dry film thickness of 1.0 μm is 60% or more and less than 99%.   10. The black matrix according to claim 7, wherein an optical density at a dry film thickness of 1.0 μm is 1.30 or more. A driving substrate of a thin film transistor (TFT) type color liquid crystal display device comprising the black matrix according to claim 7.