A pigment dispersion composition for black matrix, a production method and use thereof

Abstract

The application discloses a pigment dispersion composition for a black matrix, and preparation raw materials include, in percentage by weight, 15-30% of black pigment, 5-8% of dispersion aid, 5-15% of alkali-soluble resin, 0.2-0.6% of surfactant, 0.6-2% of silicon dioxide, and solvent supplementing to 100%. The black pigment includes carbon black and lactam black. The application adopts the combination of carbon black and lactam black with pH of 1-4, forms the pigment dispersion composition for the black matrix with good linearity, high OD value of light shielding property, high stability of the formed pigment dispersion composition, and white defects not easy to be generated in spin coating.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of photosensitive material, in particular to a pigment dispersion composition for black matrix, and a preparation method and application thereof. BACKGROUND

[0002] The pigment dispersion composition for black matrix is an important material for producing black matrix photoresist. The traditional pigment dispersion composition uses inorganic aluminum salt to wash carbon black, and then filters and dries, which is a complicated process. Moreover, a sulfonic acid-based compound pigment dispersant is introduced to prepare the black matrix photoresist material, which has poor straight linearity. In actual production process, in order to reduce the cost, the manufacturers generally bake a plurality of glass substrates coated with black photoresist together, which needs a long open time and excellent coating property, otherwise, coating white defects are easily generated. Therefore, it is very important to develop a pigment dispersion composition for black matrix, which has high resistance, high coating property, and excellent optical density and fine line adhesion.

[0003] Chinese patent CN113641080A discloses a pigment dispersion composition for black matrix and a pigment dispersion photoresist composition for black matrix, which contains carbon black and / or lactam black, a pigment dispersant containing basic groups, an alkali-soluble resin, and a solvent, and further contains inorganic compounds of barium titanate, aluminum oxide and aluminum hydroxide, which has excellent dispersion stability and can prepare a developing solution with good reusability, but its straight linearity is insufficient. Chinese patent CN108628098A discloses a black photosensitive resin composition, a color filter, and a display device comprising the color filter, the black photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, by optimizing the alkali-soluble resin, the known black pigment can be used without limitation, which is used for preparing a black matrix of a liquid crystal display device, but the process is complicated and the cost is high. SUMMARY

[0004] In order to develop a pigment dispersion composition for black matrix with high resistance, high coating property, and excellent optical density and fine line adhesion, the first aspect of the present application provides a pigment dispersion composition for black matrix, the preparation raw materials include, in terms of weight percentage, 15-30% of black pigment, 5-8% of dispersion aid, 5-15% of alkali-soluble resin, 0.2-0.6% of surfactant, 0.6-2% of silicon dioxide, and the solvent is supplemented to 100%; the black pigment includes carbon black and lactam black.

[0005] As an implementation manner, the D50 particle size of the lactam black is 70-130 nm, and the D90 particle size of the lactam black is 160-300 nm.

[0006] As an embodiment, the D50 particle size of the lactam black is 85-115 nm, and the D90 particle size of the lactam black is 180-280 nm.

[0007] As an embodiment, the carbon black is an acidic carbon black, and the weight ratio of the carbon black to the lactam black is (15-20):(1-8).

[0008] As an embodiment, the carbon black is an acidic carbon black, and the weight ratio of the carbon black to the lactam black is (16-20):(2-6).

[0009] As an embodiment, the carbon black is an acidic carbon black, and the weight ratio of the carbon black to the lactam black is 19.5:5.

[0010] As an embodiment, the pH of the acidic carbon black is 1-4.

[0011] As an embodiment, the model of the acidic carbon black includes at least one of Mogul-E, Mogul-L, TPK1104R, TPK1227R, TPK1099R manufactured by Cabot Corporation, Raven965, 5000, 1040, 1060, 1080 manufactured by Boral Corporation, NEROX3500, NEROX505, Special Black550, Special Black 4 manufactured by Orion Engineered Carbons.

[0012] In the present application, the combination of the carbon black with a pH of 1-4 and the lactam black is adopted, the black matrix formed by the pigment dispersion composition has good linearity and high OD value of light shielding, and the reason may be that the lactam black has lower conductivity, high optical density and neutral black tone, thereby having high thermal stability and good dispersion rheology, allowing a wider range of grinding process, and after being combined with the carbon black, the pigment dispersion composition formed is not easy to settle, the settlement of the carbon black is reduced, thereby having higher light shielding OD value and less linearity defects.

[0013] As an embodiment, the dispersing aid includes a basic group-containing dispersing aid and an acidic group-containing dispersing aid, and the amine value of the basic group-containing dispersing aid is 5-50 mgKOH / g.

[0014] As an embodiment, the amine value of the basic group-containing dispersing aid is 5-35 mgKOH / g.

[0015] As an embodiment, the basic group-containing dispersing aid is a high molecular basic group-containing dispersing aid. The high molecular basic group-containing dispersing aid includes at least one of a polyester-based, an acrylic-based, and an urethane-based high molecular basic group-containing dispersing aid.

[0016] As one embodiment, the high-molecular dispersing aid containing a basic group is a urethane-based dispersant.

[0017] As one embodiment, the urethane-based dispersant has a molecular weight of 300 to 10,000.

[0018] As one embodiment, the urethane-based dispersant has a molecular weight of 300 to 6,000.

[0019] As one embodiment, the urethane-based dispersant includes at least one of Disperbyk 161, Disperbyk 162, Disperbyk 167, Disperbyk 168, Disperbyk 182, Disperbyk 2163, Disperbyk 2164 by BYK-Chemie.

[0020] As one embodiment, the dispersing aid containing an acidic group includes at least one of a dispersing aid of azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxazine-based, anthraquinone-based, indanthrone-based, pyrene-based, perinone-based, diketopyrrolopyrrole-based, dioxazine-based compounds.

[0021] As one embodiment, the alkali-soluble resin has an acid value of 10 to 300 mgKOH / g and a molecular weight of <100,000.

[0022] As one embodiment, the alkali-soluble resin has an acid value of 20 to 200 mgKOH / g and a molecular weight of <50,000.

[0023] As one embodiment, the alkali-soluble resin includes at least one of an alkali-soluble polybenzoxazole resin, an alkali-soluble polybenzoxazole precursor, an alkali-soluble KAYARAD resin, an alkali-soluble epoxy (meth)acrylate resin, an alkali-soluble polysiloxane resin, an alkali-soluble phenol resin, an alkali-soluble (meth)acrylic resin, an alkali-soluble polyamine ester resin, and an alkali-soluble polyester resin.

[0024] As one embodiment, the alkali-soluble resin includes at least one of an alkali-soluble KAYARAD resin (an alkali-soluble resin containing a KAYARAD skeleton, the KAYARAD skeleton: a skeleton in which 2 aromatic groups are bonded to a quaternary carbon atom of a ring carbon atom constituting a cyclic structure via a single bond) and an alkali-soluble epoxy (meth)acrylate resin.

[0025] As an embodiment, the model of the alkali-soluble cadmium resin includes at least one of ADEKA ARKLS WR-301 manufactured by ADEKA Company; KBR-301, KBR-201, KBR-101 manufactured by KISCO Company; OGSOL CR-TR1, CR-TR2, CR-TR3, CR-TR4, CR-TR5, CR-TR6 manufactured by Osaka Gas Chemicals Co., Ltd. Company; TR-B201, B202, B102 manufactured by Changzhou Qiangli Company.

[0026] As an embodiment, the surfactant is a non-ionic surfactant, which is a fluorine-based or silicone-based surfactant.

[0027] As an embodiment, the model of the surfactant includes at least one of BYK-300, BYK-325, BYK-330 manufactured by BYK-chemical; F-470, F-475, F-478, F-554, F-559 manufactured by DIC, Japan.

[0028] As an embodiment, the particle size of the silica is 5-200 nm.

[0029] As an embodiment, the particle size of the silica is 10-150 nm.

[0030] As an embodiment, the weight ratio of the black pigment to the silica is (20-25):(0.6-2.2).

[0031] As an embodiment, the weight ratio of the black pigment to the silica is (22-25):(0.8-2.0).

[0032] As an embodiment, the weight ratio of the black pigment to the silica is 24.5:1.2.

[0033] As an embodiment, the model of the silica includes at least one of AEROSIL 380, AEROSIL 300, AEROSIL R106, AEROSIL 202, AEROSIL 812 manufactured by WACKER; CAB-O-SIL M5, CAB-O-SIL TS720 manufactured by CABOT; HDK N20, HDK H17, HDK V16 manufactured by WACKER, Germany.

[0034] The carbon black, the lactam black and the silicon dioxide in the present application form a pigment dispersion composition with high stability in the preferred weight ratio, and the spin coating is not prone to white defects, which may be due to the fact that the carbon black, the lactam black and the silicon dioxide in the preferred weight ratio make the pigment not prone to sedimentation and uniformly dispersed, and when the pigment dispersion composition is applied to the black matrix photoresist, the viscosity is suitable and the coating property is good.

[0035] As an embodiment, the solvent has a boiling point of 100-250°C.

[0036] As an embodiment, the solvent has a boiling point of 120-230°C.

[0037] As an embodiment, the solvent includes at least one of an ester-based solvent, an ether-based solvent, an ether ester-based solvent, a ketone-based solvent, an aromatic hydrocarbon solvent and a nitrogen-based solvent.

[0038] As an embodiment, the solvent is an ether ester-based solvent.

[0039] As an embodiment, the ether ester-based solvent includes at least one of propylene glycol monomethyl ether or propylene glycol methyl ether acetate.

[0040] The second aspect of the present application provides a preparation method of a pigment dispersion composition for black matrix, including the following steps:

[0041] The raw materials are mixed and stirred uniformly, coarsely ground by a rotor with a size of 0.3-0.5 mm, filtered, and finely ground by a rotor with a size of 0.1-0.2 mm to obtain the pigment dispersion composition for black matrix.

[0042] As an embodiment, the coarsely grinding is performed by a grinder without a separator, the rotor is a zirconia bead, the filling amount of the zirconia bead is 80-90 wt%, the air humidity is 50-70 RH%, the temperature is 15-30°C, the grinding rotation speed is 1300-1800 rpm, the grinding flow rate is 1-1.5 kg / min, and the grinding time is 2-4 h.

[0043] As an embodiment, the diameter of the zirconia bead is 0.3 mm, the filling amount of the zirconia bead is 85 wt%, the air humidity is 50-60 RH%, the temperature is 15-30°C, the grinding rotation speed is 1500 rpm, the grinding flow rate is 1.2 kg / min, and the grinding time is 3 h.

[0044] As an embodiment, the filtering is performed by a PP filter paper with a pore size of 1 μm.

[0045] As an embodiment, the fine grinding is performed by using a grinder with a separator, the rotor is zirconium oxide beads, the filling amount of the zirconium oxide beads is 80-90wt%, the gap of the grinder separator is 0.03-0.07mm, the air humidity is 50-70RH%, the temperature is 15-30℃, the grinding rotation speed is 1300-1800rpm, the grinding flow is 1-1.5kg / min, and the grinding time is 2-4h.

[0046] As an embodiment, the diameter of the zirconium oxide beads is 0.1mm, the filling amount of the zirconium oxide beads is 85wt%, the gap of the grinder separator is 0.05mm, the air humidity is 60RH%, the temperature is 15-30℃, the grinding rotation speed is 1500rpm, the grinding flow is 1.2kg / min, and the grinding time is 3h.

[0047] The third aspect of the present application provides a black matrix photoresist prepared by using the above-mentioned pigment dispersion composition for black matrix.

[0048] As an embodiment, the preparation raw material of the black matrix photoresist comprises, by weight percentage, 40-50% of the pigment dispersion composition for black matrix, 1-5% of a photopolymerization initiator, 1-5% of a photopolymerizable monomer, 3-8% of an alkali-soluble cadot resin, and solvent supplementing to 100%.

[0049] Compared with the prior art, the present application has the following beneficial effects:

[0050] (1) The pigment dispersion composition for black matrix of the present application uses the combination of carbon black and lactam black with pH of 1-4, and the formed pigment dispersion composition for black matrix has good linearity and high OD value of light shielding property.

[0051] (2) The pigment dispersion composition for black matrix of the present application has high stability, and white spots are not easily generated during spin coating, because carbon black, lactam black and silicon dioxide are in the preferred weight ratio.

[0052] (3) The pigment dispersion composition for black matrix of the present application uses a high-molecular dispersing aid containing basic groups, which can reduce the viscosity of the pigment dispersion composition and improve the light shielding property of the black matrix photoresist.

[0053] (4) The black matrix photoresist formed by using the alkali-soluble cadot resin of the pigment dispersion composition for black matrix of the present application has good heat resistance, and the solubility of the exposed part and the non-exposed part to alkali development changes, which is good for implementation and application.

[0054] (5) The preparation method of the pigment dispersion composition for black matrix of the present application first performs coarse grinding and then fine grinding, and the grinding is performed in a high-humidity environment, so the dispersion stability is high, the pigment dispersion composition is not easily settled, and the impedance of the black matrix photoresist is large. DETAILED DESCRIPTION

[0055] EMBODIMENT

[0056] A pigment dispersion composition for a black matrix, raw materials for preparation are shown in Table 1 in terms of weight percentage.

[0057] Table 1

[0058]

[0059] Comparative Example

[0060] A pigment dispersion composition for a black matrix, raw materials for preparation are shown in Table 2 in terms of weight percentage.

[0061] Table 2

[0062]

[0063] The D50 particle size of the lactam black is 85-115 nm, and the D90 particle size is 180-280 nm, which is purchased from basf company, and the brand is Black S0100CF.

[0064] The carbon black is an acid carbon black, and the pH is 2.5-3.3.

[0065] The dispersing aid includes a basic group-containing dispersing aid and an acid group-containing dispersing aid;

[0066] The basic group-containing dispersing aid is a urethane-based dispersant, the amine value is 5-35 mgKOH / g, the molecular weight is 300-6000, the solid content is 52%, which is purchased from BYK CHEMICAL, and the brand is Disperbyk167.

[0067] The acid group-containing dispersing aid is Lubrizol 5000S.

[0068] The alkali-soluble resin is an alkali-soluble cadot resin, the acid value is 20-200 mgKOH / g, the molecular weight of the alkali-soluble resin is <50000, and the solid content is 45%, which is purchased from KISCO company, and the brand is KBR-301.

[0069] The surfactant is a non-ionic surfactant, which is a silicone-based surfactant, which is purchased from BYK CHEMICAL, and the brand is Byk330 and Byk3500.

[0070] The particle size of the silicon dioxide is 10-20 nm, which is purchased from DEGUSSA, and the brand is silicon dioxide.

[0071] The solvent is propylene glycol methyl ether acetate.

[0072] A method for preparing a pigment dispersion composition for a black matrix, comprising the following steps:

[0073] The raw materials are mixed and stirred uniformly, coarsely ground using a rotor of 0.3 mm, and then finely ground using a rotor of 0.1 mm after filtration, to obtain the pigment dispersion composition for a black matrix.

[0074] The coarsely grinding is performed using a grinder without a separator, the rotor is zirconia beads, the filling amount of the zirconia beads is 85 wt%, the air humidity is 50-60 RH%, the temperature is 15-30°C, the grinding speed is 1500 rpm, the grinding flow is 1.2 kg / min, and the grinding time is 3 h.

[0075] The filtration is performed using a PP filter paper with a pore size of 1 μm.

[0076] The finely grinding is performed using a grinder with a separator, the rotor is zirconia beads, the filling amount of the zirconia beads is 85 wt%, the gap of the grinder separator is 0.05 mm, the air humidity is 60 RH%, the temperature is 15-30°C, the grinding speed is 1500 rpm, the grinding flow is 1.2 kg / min, and the grinding time is 3 h.

[0077] Application Example 1

[0078] A black matrix photoresist, the raw materials for preparation include, by weight percentage: a pigment dispersion composition for a black matrix 45%, a photopolymerization initiator 1%, a photopolymerizable monomer 2.5%, an alkali-soluble cadot resin 5.6%, and a solvent to make up to 100%.

[0079] The pigment dispersion composition for a black matrix is prepared according to Example 1.

[0080] The photopolymerization initiator is purchased from Changzhou Qiangli Electronics New Material Co., Ltd., and the model number is TR-PBG-304;

[0081] The photopolymerizable monomer is dipentaerythritol hexaacrylate (DPHA);

[0082] The alkali-soluble cadot resin has a solid content of 44%, is purchased from ADEKA Co., Ltd., and the model number is WR-301.

[0083] The solvent is propylene glycol methyl ether acetate.

[0084] A method for preparing a black matrix photoresist, comprising the following steps: mixing and stirring the raw materials for preparation uniformly to obtain the black matrix photoresist.

[0085] Application Example 2

[0086] A black matrix resist, the detailed description is same as application example 1, the difference is that the pigment dispersion composition for the black matrix is prepared in example 2.

[0087] Application Example 3

[0088] A black matrix resist, the detailed description is same as application example 1, the difference is that the pigment dispersion composition for the black matrix is prepared in example 3.

[0089] Application Example 4

[0090] A black matrix resist, the detailed description is same as application example 1, the difference is that the pigment dispersion composition for the black matrix is prepared in example 4.

[0091] Application Example 5

[0092] A black matrix resist, the detailed description is same as application example 1, the difference is that the pigment dispersion composition for the black matrix is prepared in example 5.

[0093] Application Example 6

[0094] A black matrix resist, the detailed description is same as application example 1, the difference is that the pigment dispersion composition for the black matrix is prepared in comparative example 1.

[0095] Application Example 7

[0096] A black matrix resist, the detailed description is same as application example 1, the difference is that the pigment dispersion composition for the black matrix is prepared in comparative example 2.

[0097] Application Example 8

[0098] A black matrix resist, the detailed description is same as application example 1, the difference is that the pigment dispersion composition for the black matrix is prepared in comparative example 3.

[0099] Application Example 9

[0100] A black matrix resist, the detailed description is same as application example 1, the difference is that the pigment dispersion composition for the black matrix is prepared in comparative example 4.

[0101] Performance Test

[0102] 1. OD value (optical density)

[0103] Each black matrix photoresist was spin-coated onto a glass substrate to obtain a 1 μm thick photoresist film. After pre-baking at 100°C for 3 minutes, it was exposed using a high-pressure mercury lamp and further baked at 230°C for 3 hours. The OD value (optical density) of each solid portion of the photoresist film was measured using a Macbeth density meter (TD-931, trade name, manufactured by Macbeth Corporation). The OD values ​​at eight locations were measured and corrected using film thickness and pigment concentration. The average OD value excluding the maximum and minimum values ​​was taken as the optical density. Additionally, the coating was cut using a dicing tool, and the film thickness at the OD value measurement points was measured. An OD value of 4.0 or higher was considered acceptable.

[0104] Corrected OD value = Measured OD value × 15.0 / Pigment concentration × 1.0 / Measured film thickness

[0105] 2. Linearity assessment:

[0106] Each black matrix photoresist was spin-coated onto a glass substrate. After heat curing, the resulting coating thickness was 1.2 μm. The coating was then dried under reduced pressure at 100 Pa for 60 s, followed by drying at 100 °C for 120 s using a hot plate. For the resulting coating, a photomask with openings of 1-20 μm linewidth every 1 μm was used as the photomask, with an intensity of 60 mW / cm² at a wavelength of 365 nm. 2 Ultraviolet radiation, with an exposure dose of 40 mJ / cm 2 Exposure was performed using the following method. Then, a developer solution consisting of 0.04 wt% KOH (potassium hydroxide) aqueous solution was used. After spray development at 23°C and a water pressure of 0.05 MPa, development was stopped with pure water, and the substrate was rinsed with a water rinse spray. After pattern development, the glass substrate was observed using an optical microscope, and the linearity of the pattern corresponding to the 6 μm opening of the photomask was evaluated according to the following criteria.

[0107] A: No defects; B: 2-3 defects are visible; C: Many defects are visible.

[0108] 3. Stability

[0109] The pigment dispersion compositions for black matrix prepared in each example and comparative example were placed in glass bottles, sealed, and stored at 60°C for 7 days. Before and after storage, the viscosity at 25°C was measured using a Borelfeld viscometer, and the viscosity change rate was calculated. The results were evaluated according to the following criteria: Viscosity change rate = [(Viscosity after 7 days of storage - Viscosity before storage) / (Viscosity before storage)]

[0110] ○: Viscosity change rate is less than 10%; △: Viscosity change rate exceeds 10% but is less than 20%;

[0111] ×: Viscosity change rate exceeds 20%.

[0112] 4. White void

[0113] A pigment dispersion composition for black matrix was applied to a glass substrate by a spin coater, and after drying, the film thickness was 1.2 μm. A hot plate was used for drying at 100°C for 120 seconds, and the following criteria were used for evaluation

[0114] A: no white void; B: 2 to 3 white voids were visible; C: a large number of white voids were visible.

[0115] 5. Resistance

[0116] Each black matrix photoresist was applied to a glass substrate by a spin coater to obtain a photoresist film having a thickness of 1 μm. After prebaking at 100°C for 3 minutes, exposure was performed using a high-pressure mercury lamp, and further baking was performed at 230°C for 3 hours. The surface resistance of each solid portion of the photoresist film thus obtained was measured using a microammeter R8340 and a shield box R12702A (manufactured by ADVANCE), and was greater than 10 13 This was considered to be high resistance.

[0117] The test results are shown in Table 3.

[0118] Table 3

[0119]

Claims

1. A pigment dispersion composition for black matrix, characterized in that, The raw materials for preparation include, by weight percentage, 24.5% black pigment, 5-8% dispersing agent, 5-15% alkali-soluble resin, 0.2-0.6% surfactant, 1.2% silica, and solvent to 100%; the black pigment includes carbon black and lactam black. The carbon black is acidic carbon black, and the weight ratio of the carbon black to lactam black is 19.5:

5. The D50 particle size of the lactam black is 70-130 nm, and the D90 particle size of the lactam black is 160-300 nm. The carbon black is selected from at least one of TPK1104R, TPK1227R, TPK1099R, NEROX3500, and SPECIAL BLACK 550; The silica is of type AEROSIL R106; The surfactant is a nonionic surfactant, and the nonionic surfactant is a fluorinated or organosilicon surfactant. The dispersing aid includes a dispersing aid containing basic groups and a dispersing aid containing acidic groups. The amine value of the dispersing aid containing basic groups is 5-35 mgKOH / g. The dispersing aid containing basic groups is a carbamate dispersant with a molecular weight of 300-6000. The method for preparing the black matrix pigment dispersion composition includes the following steps: The raw materials are mixed and stirred evenly, coarsely ground with a rotor of 0.3-0.5 mm, filtered, and then finely ground with a rotor of 0.1-0.2 mm to obtain a pigment dispersion composition for black matrix. The filtration is performed using PP filter paper with a pore size of 1μm.

2. The pigment dispersion composition for black matrix according to claim 1, characterized in that, The acid value of the alkali-soluble resin is 10-300 mg KOH / g, and the molecular weight of the alkali-soluble resin is <100,000.

3. A method for preparing a pigment dispersion composition for a black matrix according to any one of claims 1-2, characterized in that, Includes the following steps: The raw materials are mixed and stirred evenly, then coarsely ground with a 0.3-0.5 mm rotor, filtered, and then finely ground with a 0.1-0.2 mm rotor to obtain the pigment dispersion composition for black matrix.

4. A black matrix photoresist, characterized in that, It is prepared using the pigment dispersion composition for black matrix as described in any one of claims 1-2.

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