Pigment dispersion and photosensitive resin composition comprising same

Abstract

The present disclosure relates to a pigment dispersion comprising a polysiloxane binder, the pigment dispersion according to an embodiment having good heat resistance and dispersion stability, and being highly miscible with alkali-soluble resin such as polysiloxane. Thus the dispersion can be effectively used in the production of black matrix for liquid crystal display devices, column spacers, black banks for organic light emitting devices, and the like.

Description

Pigment dispersion and photosensitive resin composition containing the same

[0001] The present disclosure relates to a pigment dispersion and a photosensitive resin composition comprising the same.

[0002] Flat panel displays are widely used in smartphones, tablet PCs, and televisions, and are classified into liquid crystal displays (LCDs), organic light emitting displays (OLEDs), plasma display panels (PDPs), and electrophoretic displays depending on the light emitting method.

[0003] Liquid crystal displays (LCDs) are gaining popularity as display devices used in mobile devices, computer monitors, and HDTVs. To maintain a consistent gap between the upper and lower transparent substrates in the liquid crystal cells of an LCD, column spacers formed using a photosensitive resin composition are used. These column spacers are manufactured by applying the photosensitive resin composition onto a substrate, exposing it to active lines using a mask, and then developing and curing the resulting spacers. Furthermore, in devices such as smartphones, tablets, and OLED TVs that utilize flexible organic light-emitting diodes (OLEDs), there is a growing need to develop materials and processes for producing black banks that can effectively reduce external light reflection and improve contrast ratio and luminous efficiency without the use of polarizing films. These black banks improve the visibility of OLEDs and can function not only as banks but also as black matrices, enabling the creation of Pol-less (non-polarizing plate) and BM-less (non-black matrix) OLED devices, simplifying the manufacturing process. As a result, the use of black banks enables price competitiveness, and the technology for applying black banks is attracting attention as a useful new technology in the OLED market.

[0004] In order to improve the miscibility or heat resistance with polysiloxane, the known conventional technologies so far mainly disclose technologies that apply compounds having an ethylenically unsaturated group and an isocyanate group, polyamines having at least one secondary amino group and at least one tertiary amino group, and polyamic acids having no primary amino group. However, a technology for dispersing carbon black and coloring pigments using a polymer dispersion resin using polysiloxane is not yet known.

[0005] One embodiment is to provide a pigment dispersion having excellent heat resistance and dispersion stability.

[0006] Another embodiment is to provide a photosensitive resin composition including the pigment dispersion and a black column spacer for a liquid crystal display device and a black bank for an organic light-emitting device manufactured by curing the same.

[0007] One embodiment provides a pigment dispersion comprising a pigment, a dispersant, and a binder comprising a polysiloxane compound polymerized from a monomer comprising a compound represented by the following chemical formula 1.

[0008] [Chemical Formula 1]

[0009] (R 1 ) a Si(OR 2 ) 4-a

[0010] In the above chemical formula 1,

[0011] R 1 are each independently hydrogen, C 1-20 Alkyl group, C 2-20 Alkenyl group, or C 6-20 It is an aryl group,

[0012] R 2 are each independently hydrogen, C 1-20 Alkyl group, C 1-20 Asilgi, or C 6-20 It is an aryl group,

[0013] a is an integer from 0 to 3.

[0014] Another embodiment provides a photosensitive resin composition comprising a pigment dispersion according to the above embodiment.

[0015] Another embodiment provides a black column spacer for a liquid crystal display device and a black bank for an organic light-emitting device manufactured by curing a photosensitive resin composition according to the above embodiment.

[0016] The present disclosure relates to a pigment dispersion comprising a polysiloxane binder, and the pigment dispersion according to one embodiment has excellent heat resistance and dispersion stability, and excellent miscibility with an alkaline-soluble resin such as polysiloxane, and therefore can be usefully used in the manufacture of a black matrix for a liquid crystal display, a column spacer, or a black bank for an organic light-emitting device.

[0017] The embodiments described in this specification may be modified in many different forms, and thus the technology according to one implementation is not limited to the embodiments described below. Furthermore, throughout the specification, the terms "comprising," "including," "containing," "includes," or "having" a component do not exclude other components unless specifically stated to the contrary, but rather mean that other components may be included, and do not exclude additional elements, materials, or processes that are not listed.

[0018] The numerical ranges used herein include the lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of the upper and lower limits of numerical ranges defined in different shapes. For example, if the content of a composition is defined as 10% to 80% or 20% to 50%, the numerical ranges of 10% to 50% or 50% to 80% should also be interpreted as being described herein. Unless otherwise specified herein, values ​​outside the numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0019] Unless otherwise specifically defined herein, “about” may be considered a value within 30%, 25%, 20%, 15%, 10%, 5%, 3%, 2%, 1% or 0.5% of the stated value.

[0020] The term "alkylene group" as used herein refers to a straight or branched carbon-carbon saturated bond diradical, which may be substituted with any substituent. The term "alkenylene group" as used herein refers to a straight or branched carbon-carbon chain diradical containing one or more carbon-carbon unsaturated bonds (double bonds), which may be substituted with any substituent. The term "alkynylene group" as used herein refers to a straight or branched carbon-carbon chain diradical containing one or more carbon-carbon unsaturated bonds (triple bonds), which may be substituted with any substituent.

[0021] The term "alkyl group" as used herein refers to a straight or branched chain radical of carbon saturated bonds, which may be substituted with any substituent. The term "alkenyl group" as used herein refers to a straight or branched carbon chain radical containing one or more carbon unsaturated bonds (double bonds), which may be substituted with any substituent.

[0022] The term "aryl" as used herein is not limited to a bridged ring, a spiro ring, or a fused ring. For example, the aryl may be benzene, naphthalene, fluorene, anthracene, phenanthrene, bibenzene, triphenylene, pyrene, or chrysene.

[0023] Each substituent described herein has the same alphabet (R 1 , a, etc.), they are independent of each other in each chemical formula and may therefore be different from each other.

[0024] Hereinafter, the present disclosure will be described in detail (with reference to the attached drawings). However, this is merely exemplary and the present disclosure is not limited to the specific embodiments described as examples.

[0025]

[0026] One embodiment provides a pigment dispersion comprising a pigment, a dispersant, and a binder comprising a polysiloxane compound polymerized from a monomer comprising a compound represented by the following chemical formula 1.

[0027] [Chemical Formula 1]

[0028] (R 1 ) a Si(OR 2 ) 4-a

[0029] In the above chemical formula 1,

[0030] R 1 are each independently hydrogen, C 1-20 Alkyl group, C 2-20 Alkenyl group, or C 6-20 It is an aryl group,

[0031] R 2 are each independently hydrogen, C 1-20 Alkyl group, C 1-20 Asilgi, or C 6-20 It is an aryl group,

[0032] a is an integer from 0 to 4.

[0033] In one embodiment, R of the above formula 1 1 are each independently hydrogen, C 1-10 Alkyl group, C 2-10 Alkenyl group, or C 6-10 It can be an aryl group. Or C 1-8 Alkyl group, C 1-5 Alkyl group, C 1-3 Alkyl group, C 1-2 Alkyl group, -CH3, -CH2CH3, C 2-10 Alkenyl group, C 2-8 Alkenyl group, C 2-5 Alkenyl group, C 2-3 Alkenyl group, -CHCH2, C 6-8 It can be an aryl group or a phenyl group.

[0034] In one embodiment, R of the above formula 1 2 are each independently hydrogen, C 1-10 Alkyl group, C 1-10 Asilgi, or C6-10 It can be an aryl group. Or C 1-8 Alkyl group, C 1-5 Alkyl group, C 1-3 Alkyl group, C 1-2 Alkyl group, -CH3, -CH2CH3, C 1-8 As you know, C 1-5 As you know, C 1-3 Acyl group, -COCH3, C 6-8 It can be an aryl group or a phenyl group.

[0035] In one embodiment, a in the above formula 1 may be an integer from 0 to 2, 0, 1, or 2.

[0036] As a specific example, in the chemical formula 1, R 1 is -CH3, -CH2CH3, -CHCH2, or a phenyl group; and the R 2 are each independently -CH3, or -CH2CH3; and a may be 0 or 1.

[0037] In one embodiment, the polysiloxane compound included in the binder may be polymerized using two or more different compounds represented by the chemical formula 1 (specifically, two or three compounds) as monomers. This will be described below with specific examples.

[0038] The polysiloxane compound included in the above binder may be polymerized using two different silane compounds, for example, a compound represented by the following chemical formula 1-1 and a compound represented by the following chemical formula 1-2, as monomers.

[0039] [Chemical Formula 1-1]

[0040] Si(OR 11 )4

[0041] In chemical formula 1-1,

[0042] R 11 are each independently hydrogen or C 1-10 It is an alkyl group,

[0043] [Chemical Formula 1-2]

[0044] R 12 Si(OR 22 )3

[0045] In the above chemical formula 1-2,

[0046] R 12 is C 1-10 It is an alkyl group,

[0047] R 22 are each independently hydrogen or C 1-10 It is an alkyl group.

[0048] In one embodiment, the R of the above chemical formula 1-1 11 are each independently C 1-8 Alkyl group, C 1-5 Alkyl group, C 1-3 Alkyl group, C 1-2 It can be an alkyl group, -CH3, or -CH2CH3.

[0049] In one embodiment, the R of the above chemical formula 1-2 12 and R 22 are each independently C 1-8 Alkyl group, C 1-5 Alkyl group, C 1-3 Alkyl group, C 1-2 It can be an alkyl group, -CH3, or -CH2CH3.

[0050] Alternatively, the polysiloxane compound included in the binder may be polymerized using three different silane compounds, for example, a compound represented by the following chemical formula 1-1, a compound represented by the following chemical formula 1-2, and a compound represented by the following chemical formula 1-3, as monomers.

[0051] [Chemical Formula 1-1]

[0052] Si(OR 11 )4

[0053] In chemical formula 1-1,

[0054] R 11 are each independently hydrogen or C 1-10 It is an alkyl group,

[0055] [Chemical Formula 1-2]

[0056] R 12 Si(OR 22 )3

[0057] In the above chemical formula 1-2,

[0058] R 12 is C 1-10 It is an alkyl group,

[0059] R 22 are each independently hydrogen or C 1-10 It is an alkyl group,

[0060] [Chemical Formula 1-3]

[0061] R 13 Si(OR 23 )3

[0062] In the above chemical formula 1-3,

[0063] R 13 Silver C 1-10 Alkyl group, C 2-10 Alkenyl group, or C 6-10 It is an aryl group,

[0064] R 23 are each independently hydrogen or C 1-10 It is an alkyl group.

[0065] As described above for the substituents of the above chemical formulas 1-1 and 1-2, in one embodiment, the R of the above chemical formula 1-3 13 Silver C 1-8 Alkyl group, C 1-5 Alkyl group, C 1-3 Alkyl group, C 1-2 Alkyl group, -CH3, -CH2CH3, C 2-10 Alkenyl group, C 2-8 Alkenyl group, C 2-5 Alkenyl group, C 2-3 Alkenyl group, -CHCH2, C 6-8 It can be an aryl group or a phenyl group.

[0066] In one embodiment, the R of the above chemical formula 1-3 23 are each independently C 1-8 Alkyl group, C 1-5 Alkyl group, C 1-3 Alkyl group, C1-2 It can be an alkyl group, -CH3, or -CH2CH3.

[0067] In one embodiment, specific examples of the silane compound represented by the above chemical formula 1 include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-Acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, Examples include trifunctional silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; bifunctional silanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, and (3-glycidoxypropyl)methyldiethoxysilane; and monofunctional silanes such as trimethylmethoxysilane, tri n-butylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, and (3-glycidoxypropyl)dimethylethoxysilane.

[0068] In one embodiment, the polysiloxane compound may include a repeating unit represented by the following chemical formula 11 or chemical formula 12.

[0069] [Chemical Formula 11]

[0070]

[0071] [Chemical Formula 12]

[0072]

[0073] In the above chemical formulas 11 and 12, x and y are real numbers satisfying 0 < x < 1 and 0 < y < 1, and A is a substituent.

[0074] Or in one embodiment, the polysiloxane compound may be a straight-chain polysiloxane, for example, 1,1,3,3-tetramethyl-1,3-dimethoxydisiloxane, 1,1,3,3-tetramethyl-1,3-diethoxydisiloxane, 1,1,3,3-tetraethyl-1,3-dimethoxydisiloxane, 1,1,3,3-tetraethyl-1,3-diethoxydisiloxane, silanol-terminated polydimethylsiloxane (hereinafter referred to as a trade name) manufactured by Gerest Corporation shown below "DMS-S12" (molecular weight 400 to 700), "DMS-S15" (molecular weight 1500 to 2000), "DMS-S21" (molecular weight 4200), "DMS-S27" (molecular weight 18000), "DMS-S31" (molecular weight 26000), "DMS-S32" (molecular weight 36000), "DMS-S33" (molecular weight 43500), "DMS-S35" (molecular weight 49000), "DMS-S38" (molecular weight 58000), "DMS-S42" (molecular weight 77000), the silanol-terminated diphenylsiloxane-dimethylsiloxane copolymer "PSD-0332" (molecular weight 35000, copolymerized with 2.5 to 3.5 mol% of diphenylsiloxane), "PDS-1615" (molecular weight 900 to 1000, copolymerized with 14 to 18 mol% of diphenylsiloxane), the silanol-terminated polydiphenylsiloxane "PDS-9931" (molecular weight 1000 to 1400) can be mentioned. In addition, these straight-chain polysiloxanes can be used alone or in combination of two or more. In some embodiments, the use of straight-chain polysiloxanes can improve the storage stability of the composition. This is because the straight-chain portions exist in a crosslinked manner, making it difficult for unreacted silanol groups to approach each other, and making it difficult for a condensation reaction between dispersed binders, which is a side reaction during the production of a colored pigment composition, to occur.

[0075] The above polysiloxane compound is obtained by hydrolysis and condensation of a monomer represented by Chemical Formula 1, and hydrolysis and partial condensation can be performed using a general method. For example, a solvent, water, and, if necessary, a catalyst are added to the mixture, and the mixture is heated and stirred at 50°C to 150°C for 0.5 to 100 hours. In addition, during stirring, if necessary, the hydrolysis by-product (alcohol such as methanol) or condensation by-product (water) can be distilled off. The reaction solvent is not particularly limited, but the same solvent as described below is usually used. The amount of water added for the hydrolysis reaction is preferably 0.5 to 2 mol per 1 mol of the hydrolyzable group. The catalyst added if necessary is not particularly limited, but an acid catalyst or a base catalyst is preferably used. Specific examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polyhydric carboxylic acids or their anhydrides, and ion exchange resins. Specific examples of base catalysts include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, alkoxysilanes having amino groups, and ion exchange resins. The amount of catalyst added is preferably 0.01 to 10 parts by weight per 100 parts by weight of the mixture of organosilane and linear polysiloxane.

[0076] In addition, from the viewpoint of storage stability of the dispersion, it is preferable that the siloxane polymer solution after hydrolysis and partial condensation does not contain a catalyst, and the catalyst can be removed as needed. The method for removing the catalyst is not particularly limited, but a method using water washing or an ion exchange resin is preferable. Water washing is a method in which the siloxane polymer solution is diluted with a suitable hydrophobic solvent, then washed several times with water, and the resulting organic layer is concentrated in an evaporator. The method for removing using an ion exchange resin is a method in which the siloxane polymer solution is brought into contact with a suitable ion exchange resin.

[0077] In one embodiment, the binder may be present in an amount of from 70 wt % to 99 wt %, from 75 wt % to 99 wt %, from 80 wt % to 95 wt %, from 80 wt % to 90 wt %, or about 85 wt %, based on the total weight of the pigment, binder, and dispersant.

[0078] In one embodiment, the pigment may be included in an amount of 1 wt% to 20 wt%, 5 wt% to 15 wt%, 6 wt% to 12 wt%, or about 9 wt%, based on the total weight of the pigment, binder, and dispersant. The pigment is not particularly limited, but may be, for example, an inorganic pigment, an organic pigment, or a composite pigment thereof. When the pigment is a composite pigment, the inorganic pigment and the organic pigment may be composited in a mass ratio of 1:3 to 3:1. The composite pigment may be prepared by depositing an organic pigment or carbon black on an inorganic pigment particle, or by mechanochemically mixing and grinding an inorganic pigment and an organic pigment or carbon black. At this time, the adhesive strength of the organic pigment and the inorganic pigment may be enhanced by placing a layer of an organosilane compound formed from polysiloxane or alkylsilane therebetween, if necessary.

[0079] Examples of the above organic pigments include aniline black as a black pigment; and anthraquinone, phthalocyanine blue, phthalocyanine green, diazo- or monoazo yellow pigments, disazo yellow pigments, pyranthrome, perylene, heterocyclic yellow, quinacridone, (thio)indigo, etc. as color pigments. Among these, phthalocyanine pigments, quinacridone pigments, monoazo yellow pigments, disazo yellow pigments, and heterocyclic yellow pigments are particularly preferable in terms of color development properties. Examples of the above phthalocyanine pigments include copper phthalocyanine blue or a derivative thereof (CI Pigment Blue 15:3, 15:4), aluminum phthalocyanine, etc.

[0080] Examples of the above quinacridone pigments include CI Pigment Orange 48, CI Pigment Orange 49, CI Pigment Red 122, CI Pigment Red 192, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Violet 19, and CI Pigment Violet 42.

[0081] Examples of the above monoazo yellow pigments include CI Pigment Yellow 74, CI Pigment Yellow 109, CI Pigment Yellow 128, and CI Pigment Yellow 151.

[0082] Examples of the above disazo yellow pigments include CI Pigment Yellow 14, CI Pigment Yellow 16, and CI Pigment Yellow 17.

[0083] Examples of the above complex ring yellow pigments include CI Pigment Yellow 117 and CI Pigment Yellow 138.

[0084] The particle shape of the organic pigment particles is preferably a small aspect ratio, most preferably a spherical shape. In addition, the color of the inorganic pigment particles is preferably transparent or white when coloring the pigment, and when depositing a black colorant, a black inorganic pigment is acceptable. The primary particle size of the inorganic pigment particles is preferably 100 nm or less, or 5 nm to 50 nm.

[0085] The mass ratio of the above-mentioned inorganic pigment particles to the colorant as the organic pigment or carbon black (i.e., inorganic pigment particles: colorant) is preferably 3:1 to 1:3, more preferably 3:2 to 1:2. If the mass ratio of the colorant is low, the color development ability or coloring ability may be reduced, and if the amount of the colorant is excessively large, the transparency and color tone may be poor. Examples of colorant particles in which such inorganic pigment particles are coated with organic pigments or carbon black include composite materials such as silica / carbon black composite materials, silica / phthalocyanine CI PB 15:3 composite materials, silica / disazo yellow composite materials, and silica / quinacridone CIPR122 composite materials (manufactured by Toda Industries, Ltd.). The primary particle size of the above-mentioned material is sufficiently small for suitable use. Here, when inorganic pigment particles having a primary particle size of 20 nm are coated with an equivalent amount of organic pigment, the primary particle size of the pigment becomes approximately 25 nm. If the pigment can be dispersed down to the primary particles using an appropriate dispersant, an extremely fine pigment dispersion ink with a dispersed particle size of 25 nm can be produced. In the composite pigment, not only the organic pigment on the surface contributes to dispersion, but also the characteristics of the central inorganic pigment are exhibited through a thin layer of approximately 2.5 nm in thickness. Therefore, the pigment dispersant must be selected based on both the organic and inorganic pigments.

[0086] In one embodiment, the pigment may be, for example, black, blue, red, purple, or orange.

[0087] In one embodiment, the particles included in the pigment dispersion may have an average particle diameter of 50 nm to 200 nm. The particles may include a pigment and / or a binder.

[0088] In one embodiment, the pigment can be made hydrophilic by treating the particle surface with a carboxyl group, a carbonyl group, a sulfonic group, or a hydroxyl group through oxidation treatment, an azo reaction, or a plasma treatment, thereby improving aqueous dispersibility.

[0089] In one embodiment, the pigment dispersion may further comprise a dye, such as an inorganic dye or an organic dye.

[0090] In one embodiment, the weight average molecular weight of the polysiloxane compound is not particularly limited, but may be, for example, 1,000 g / mol to 100,000 g / mol, 1,000 g / mol to 80,000 g / mol, or 2,000 g / mol to 60,000 g / mol. The weight average molecular weight may be, for example, a polystyrene conversion standard measured by GPC (gel permeation chromatography). When the weight average molecular weight of the binder is 1,000 g / mol or less, dispersibility and miscibility may deteriorate, and when it is higher than 100,000 g / mol, solubility of the composition in a developer may deteriorate during pattern formation of the final photosensitive composition.

[0091] In one embodiment, the alkaline solubility of the polysiloxane compound may be from 10 μm / sec to 10,000 μm / sec, but is not particularly limited.

[0092] According to one embodiment, the pigment dispersion may be for a black matrix.

[0093] In one embodiment, the pigment dispersion may further include a dispersant. The dispersant may be any known dispersant without limitation, and may include, for example, an acrylic, styrene, polyethyleneimine, or urethane polymer.

[0094]

[0095] Another embodiment provides a photosensitive resin composition comprising a pigment dispersion according to the above embodiment and an alkaline-soluble resin. Since the pigment dispersion is the same as the pigment dispersion described above, a detailed description thereof will be omitted.

[0096] In one embodiment, the alkali-soluble resin may be a polysiloxane resin. The polysiloxane resin is not particularly limited, but may be the same as the polysiloxane component of the binder included in the pigment dispersion. That is, it may be polymerized from a monomer represented by the following chemical formula 1, or may be polymerized using the compound represented by the chemical formula 1-1 and the compound represented by the chemical formula 1-2 as monomers, or may be polymerized using the compound represented by the chemical formula 1-1, the compound represented by the chemical formula 1-2, and the compound represented by the chemical formula 1-3 as monomers. Since this is the same as described above, a detailed description thereof will be omitted below.

[0097] [Chemical Formula 1]

[0098] (R 1 ) a Si(OR 2 ) 4-a

[0099] In the above chemical formula 1,

[0100] R 1 are each independently hydrogen, C 1-20 Alkyl group, C 2-20 Alkenyl group, or C 6-20 It is an aryl group,

[0101] R 2 are each independently hydrogen, C 1-20 Alkyl group, C1-20 Asilgi, or C 6-20 It is an aryl group,

[0102] a is an integer from 0 to 4.

[0103] In one embodiment, the photosensitive resin composition may include a surfactant. The above surfactants include, for example, BM-1000, BM-1100 (manufactured by BM CHEMIE), Megapack F142 D, Megapack F172, Megapack F173, Megapack F183, F-470, F-471, F-475, F-482, F-489 (manufactured by Dainippon Ink & Kagaku Kogyo Co., Ltd.), Florard FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufactured by Asahi Glass Co., Ltd.), F-Top EF301, F-Top 303, F-Top 352 (manufactured by Shin-Akita Kasei Co., Ltd.), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Silicone Co., Ltd.), DC3PA, DC7PA, SH11PA, SH21PA, SH8400, GE, FZ-2100, FZ-2110, FZ-2122, FZ-2222, FZ-2233 (manufactured by Dow Corning Toray Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, Fluorine-based and silicone-based surfactants such as TSF-4460, TSF-4452 (manufactured by Toshiba Silicone Co., Ltd.), and BYK-333 (manufactured by BYK Co., Ltd.); nonionic surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether, and polyoxyethylene nonylphenyl ether; and polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based copolymer Polyflow No.Examples include 57, 95 (manufactured by Kyoeisha Yuji Kagaku Kogyo Co., Ltd.). These can be used alone or in combination of two or more types.

[0104] In one embodiment, the photosensitive resin composition may include an adhesive aid. The adhesive aid may be, for example, a silane coupling agent. Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, and the like, and these may be used alone or in combination of two or more. Preferably, in terms of the film remaining ratio and adhesion to the substrate, γ-isocyanatopropyltriethoxysilane and / or N-phenyl-3-aminopropyltriethoxysilane may be used.

[0105] The pigment dispersion or photosensitive resin composition according to one embodiment may include a dispersing aid. For example, SOLSPERSE-5000, SOLSPERSE-22000, or SOLSPERSE-12000 may be used.

[0106] The pigment dispersion or photosensitive resin composition according to one embodiment may include a solvent, and for example, it is preferable to use an organic solvent suitable for compatibility with a high molecular weight copolymer solution having a pigment affinity group, good compatibility with a dispersing aid, compatibility with a photosensitive resin used in an organic black matrix, workability, etc. For example, PGMEA (Propylene Glycol Monomethyl Ether Acetate), EEP (Ethyl 3-Ethoxypropionate), ethylene glycol, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, diethylene glycol, cyclohexanone, propylene glycol methyl ether, etc. can be used, and these solvents can be used alone or in mixtures. In particular, it is preferable to use PGMEA (Propylene Glycol Monomethyl Ether Acetate) and EEP (Ethyl 3-Ethoxypropionate).

[0107] Another embodiment provides a method for preparing a pigment dispersion according to the above embodiment. The method for preparing a pigment dispersion according to one embodiment is as follows. A solvent is placed in a container and stirred at low speed at 500 to 1,800 rpm for 2 to 20 minutes with a stirrer. Then, a polysiloxane binder is added and stirred at low speed at 500 to 1,800 rpm for 5 to 20 minutes. While stirring the mixture, a pigment is added and stirred at high speed at 2,000 to 4,000 rpm for 10 to 50 minutes. Since the pigment dispersion composition according to one embodiment is introduced as a raw material used for electronic component materials, a high-pressure dispersion method is introduced that eliminates contamination of a dispersion system using a medium (glass beads, zirconium beads, etc.) and can disperse up to the primary particle size at the same time. It is designed with a completely different mechanism from the existing 3-roll mill, emulsifier, disperser and grinder, and is capable of manufacturing ultra-fine, high-particle size particles in the 1 / 100㎛ range. The dispersion method is a wet dispersion system that applies ultra-high pressure (1,000 - 3,500 kgf / ㎠) of energy to the dispersion, and divides the dispersion into two streams and recombines them, causing them to collide against each other to achieve ultra-fine atomization, emulsification and dispersion. The above-mentioned dispersion process has the advantage of having almost no wear of metal powder, wear of beads, etc., or external contamination that were problems in the existing system, and at the same time, it also has the advantage of shortening the process time and improving the quality of the product.

[0108]

[0109] Another embodiment provides a black column spacer for a liquid crystal display device or a black bank for an organic light-emitting device manufactured by curing the photosensitive resin composition according to the above embodiment.

[0110] Hereinafter, specific examples and experimental examples are provided to illustrate the present invention. However, the examples and experimental examples described below are merely illustrative of some embodiments of one implementation, and therefore, the technology described in this specification should not be construed as being limited thereto.

[0111]

[0112] <Manufacturing Example 1> Synthesis of polysiloxane compound 1

[0113] 190.3 g of vinyltriethoxysilane, 178.3 g of methyltriethoxysilane, 208.3 g of tetraethoxysilane, and 1 L of butyl acetate were placed in a three-necked flask with a volume of approximately 2 L, and a solution of 2 mL of 1 mol / L nitric acid and 180 mL of purified water was added dropwise over 30 minutes using a dropping funnel installed therein while vigorously stirring the contents of the flask. As a result, an exothermic reaction occurred in the contents of the flask, and initially, the solution was white and cloudy, but as the stirring continued, it became a colorless and transparent solution. After neutralizing the mixture, 1,000 mL of toluene and 1,000 mL of water were added, and the mixture was separated into two layers. The separated organic layer was concentrated under reduced pressure to remove the solvent. The molecular weight of the obtained polysiloxane compound was measured, and the weight average molecular weight was confirmed to be 2,500 g / mol.

[0114] <Manufacturing Example 2> Synthesis of polysiloxane compound 2

[0115] 190.3 g of phenyltriethoxysilane, 178.3 g of methyltriethoxysilane, 208.3 g of tetraethoxysilane, and 1 L of butyl acetate were placed in a three-necked flask with a volume of about 2 L, and a solution of 2 mL of 1 mol / L nitric acid and 180 mL of purified water was added dropwise over 30 minutes using a dropping funnel installed therein while vigorously stirring the contents of the flask. As a result, an exothermic reaction occurred in the contents of the flask, and initially it was a white, cloudy solution, but as the stirring continued, it became a colorless, transparent solution. After neutralizing the mixture, 1,000 mL of toluene and 1,000 mL of water were added, and the mixture was separated into two layers. The separated organic layer was concentrated under reduced pressure to remove the solvent. The molecular weight of the obtained polysiloxane compound was measured, and the weight average molecular weight was confirmed to be 55,000 g / mol.

[0116]

[0117] <Example 1> Preparation of pigment dispersion 1

[0118] As a binder, 9 g of lactam black, a black organic pigment, as a colorant, 6 g of BYK-9076, as a dispersant, and 100 g of propylene glycol-1-monomethyl ether-2-acetate were added to 85 g of polysiloxane compound 1 synthesized in the above-mentioned manufacturing example 1, and stirred with a mechanical stirrer for 1 hour. Then, zirconium beads were added in the same volume ratio as the mixed solution and dispersed at about 2,500 rpm for 2 hours to prepare a nano-sized pigment dispersion.

[0119] <Example 2> Preparation of pigment dispersion 2

[0120] A pigment dispersion was prepared in the same manner as in Example 1, except that polysiloxane compound 2 synthesized in Preparation Example 2 was used instead of polysiloxane compound 1.

[0121] <Example 3> Preparation of pigment dispersion 3

[0122] A pigment dispersion was prepared in the same manner as in Example 1 above, except that Pigment Blue 15:6, a blue organic pigment, was used instead of the black organic pigment.

[0123] <Example 4> Preparation of pigment dispersion 4

[0124] A pigment dispersion was prepared in the same manner as in Example 1 above, except that a red organic pigment, Pigment Red 291, was used instead of the black organic pigment.

[0125] <Comparative Example 1> Preparation of pigment dispersion 5

[0126] A pigment dispersion was prepared in the same manner as in Example 1 above, except that the acrylate copolymer solution DISPER BYK-2000 was used instead of polysiloxane compound 1.

[0127] <Comparative Example 2> Preparation of pigment dispersion 6

[0128] A pigment dispersion was prepared in the same manner as in Example 3 above, except that the acrylate copolymer solution DISPER BYK-2000 was used instead of polysiloxane compound 1.

[0129] <Comparative Example 3> Preparation of pigment dispersion 7

[0130] A pigment dispersion was prepared in the same manner as in Example 4 above, except that the acrylate copolymer solution DISPER BYK-2000 was used instead of polysiloxane compound 1.

[0131]

[0132] <Examples 5 to 8> Preparation of photosensitive resin compositions 1 to 4

[0133] Each of 1.5 g of the pigment dispersions 1 to 4 prepared in Examples 1 to 4, 8.24 g of the polysiloxane synthesized in Preparation Example 1, 0.042 g of a leveling surfactant (BYK 333 silicone surfactant), and 0.084 g of an adhesive aid (Shin-Etsu, KBE-9007) were added to 8.2 g of propylene glycol-1-monomethyl ether-2-acetate, and stirred to prepare a photosensitive resin composition.

[0134] <Comparative Examples 4 to 6> Preparation of photosensitive resin compositions 5 to 7

[0135] Each photosensitive resin composition was prepared in the same manner as in Examples 5 to 8, except that each pigment dispersion 5 to 7 prepared in Comparative Examples 1 to 3 was sequentially used as a pigment dispersion.

[0136]

[0137] <Experimental Example>

[0138] The photosensitive resin compositions manufactured in Examples 5 to 8 and Comparative Examples 4 to 6 were applied to a substrate using a spin coating method to a thickness of 4 μm, and then heated at a temperature of 90°C for 2 minutes to remove the solvent, thereby forming a coating film. The formed coating film was post-baked at 400°C for 30 minutes using a hot air circulation dryer to check for color change in the coating film. Next, the coating film on the substrate after the post-baking was scraped and collected in a powder state, and the weight change during that time was analyzed using a TGA device and summarized in Table 1 below.

[0139]

[0140] Color change ○: No discoloration ×: No discoloration TGA weight loss Example 5 x 2.3% Example 6 x 1.5% Example 7 x 2.8% Example 8 x 2.7% Comparative example 4 ○ 75% Comparative example 5 ○ 85% Comparative example 6 ○ 79%

[0141] As can be seen from Table 1 above, the photosensitive resin composition according to the example using the pigment dispersion containing a polysiloxane binder showed excellent compatibility with the polysiloxane resin and high heat resistance, so that even when the coated film was treated at high temperatures, there was almost no color change and durability was also excellent. On the other hand, the photosensitive resin composition according to the comparative example using the pigment dispersion containing an acrylic copolymer as a binder showed discoloration and weight change at high temperatures, and through this, it was confirmed that it was significantly inferior in high temperature durability compared to the example.

[0142]

[0143] Above, although an embodiment has been described in detail through examples and experimental examples, the scope of an embodiment is not limited to a specific example, and should be interpreted in accordance with the appended patent claims.

Claims

1. A pigment dispersion comprising a pigment, a dispersant, and a binder comprising a polysiloxane compound polymerized from a monomer comprising a compound represented by the following chemical formula 1: [Chemical Formula 1] (R 1 ) a Si(OR 2 ) 4-a In the above chemical formula 1, R 1 are each independently hydrogen, C 1-20 Alkyl group, C 2-20 Alkenyl group, or C 6-20 It is aryl, R 2 are each independently hydrogen, C 1-20 Alkyl group, C 1-20 As you know, or C 6-20 It is an aryl group, a is an integer from 0 to 3.

2. In paragraph 1, In the chemical formula 1 above, R 1 are each independently hydrogen, C 1-10 Alkyl group, C 2-10 Alkenyl group, or C 6-10 Aryl group, pigment dispersion.

3. In paragraph 1, In the chemical formula 1 above, R 2 are each independently hydrogen, C 1-10 Alkyl group, C 1-10 As you know, or C 6-10 Aryl group, pigment dispersion.

4. In paragraph 1, In the chemical formula 1 above, R 1 is -CH3, -CH2CH3, -CHCH2, or a phenyl group; and R 2 A pigment dispersion, wherein each of a is independently -CH3, or -CH2CH3; and a is 0 or 1.

5. In paragraph 1, A pigment dispersion, wherein the polysiloxane compound is polymerized from a monomer containing two or more different compounds represented by the chemical formula 1.

6. In paragraph 1, The above polysiloxane compound is a pigment dispersion polymerized using a compound represented by the following chemical formula 1-1 and a compound represented by the following chemical formula 1-2 as monomers: [Chemical Formula 1-1] Si(OR 11 )4 In chemical formula 1-1, R 11 are each independently hydrogen or C 1-10 It is an alkyl group, [Chemical Formula 1-2] R 12 Si(OR 22 )3 In the above chemical formula 1-2, R 12 is C 1-10 It is an alkyl group, R 22 are each independently hydrogen or C 1-10 It is an alkyl group.

7. In paragraph 1, The above polysiloxane compound is a pigment dispersion polymerized using a compound represented by the following chemical formula 1-1, a compound represented by the following chemical formula 1-2, and a compound represented by the following chemical formula 1-3 as monomers: [Chemical Formula 1-1] Si(OR 11 )4 In chemical formula 1-1, R 11 are each independently hydrogen or C 1-10 It is an alkyl group, [Chemical Formula 1-2] R 12 Si(OR 22 )3 In the above chemical formula 1-2, R 12 is C 1-10 It is an alkyl group, R 22 are each independently hydrogen or C 1-10 It is an alkyl group, [Chemical Formula 1-3] R 13 Si(OR 23 )3 In the above chemical formula 1-3, R 13 Silver C 1-10 Alkyl group, C 2-10 Alkenyl group, or C 6-10 It is an aryl group, R 23 are each independently hydrogen or C 1-10 It is an alkyl group.

8. In paragraph 1, A pigment dispersion, wherein the binder is contained in an amount of 70 to 99 wt% based on the total weight of the pigment, binder and dispersant.

9. In paragraph 1, A pigment dispersion, wherein the pigment is contained in an amount of 1 to 20 wt% based on the total weight of the pigment, binder and dispersant.

10. In paragraph 1, A pigment dispersion wherein the weight average molecular weight of the polysiloxane compound is 1,000 g / mol to 100,000 g / mol.

11. In paragraph 1, The above pigment is a pigment dispersion which is an inorganic pigment, an organic pigment, or a composite pigment thereof.

12. In paragraph 1, The above pigment is a pigment dispersion which is black, blue, red, purple, or orange.

13. In paragraph 1, The pigment dispersion is a pigment dispersion comprising particles having an average particle diameter of 50 nm to 200 nm.

14. In paragraph 1, A pigment dispersion having an alkaline solubility of the polysiloxane compound of 10 μm / sec to 10,000 μm / sec.

15. In paragraph 1, The above pigment dispersion is a pigment dispersion for use in a black matrix.

16. A photosensitive resin composition comprising a pigment dispersion according to any one of claims 1 to 15 and an alkali-soluble resin.

17. In paragraph 16, A photosensitive resin composition wherein the alkali-soluble resin is a polysiloxane resin.

18. In paragraph 17, The above polysiloxane resin is a photosensitive resin composition polymerized from a monomer represented by the following chemical formula 1: [Chemical Formula 1] (R 1 ) a Si(OR 2 ) 4-a In the above chemical formula 1, R 1 are each independently hydrogen, C 1-20 Alkyl group, C 2-20 Alkenyl group, or C 6-20 It is aryl, R 2 are each independently hydrogen, C 1-20 Alkyl group, C 1-20 As you know, or C 6-20 It is aryl, a is an integer from 0 to 3.

19. A black column spacer for a liquid crystal display device manufactured by curing the photosensitive resin composition according to Article 16.

20. A black bank for an organic light-emitting device manufactured by curing a photosensitive resin composition according to Article 16.

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