Alkali-soluble resin, colored photosensitive resin composition, preparation method of colored photosensitive resin composition, color filter and liquid crystal display device

Abstract

The invention provides alkali-soluble resin, a colored photosensitive resin composition, a preparation method of the colored photosensitive resin composition, a color filter and a liquid crystal display device, and relates to the field of materials. The structural general formula of the alkali-soluble resin is # imgabs0 #, R1 is any one of alkyl with the carbon atom number of 1-5 and aryl with the carbon atom number of 6-10, R2 is any one of alkyl with the carbon atom number of 1-5 and aryl with the carbon atom number of 6-10, and R3 is any one of alkyl with the carbon atom number of 1-5 and aryl with the carbon atom number of 6-10. R3 is any one of alkyl groups having 1 to 4 carbon atoms; r4 is any one of alkyl groups with 2-5 carbon atoms; v, W, X and Y are respectively independent positive integers. According to the alkali-soluble resin provided by the invention, unsaturated double bonds are cross-linked during light curing to form a compact polymer network, so that migration of metal ions in pigment particles is inhibited, and imaging equipment has an excellent voltage holding ratio.

Description

Technical Field

[0001] The present application relates to the field of materials, and in particular to an alkali-soluble resin, a colored photosensitive resin composition and a preparation method thereof, a color filter and a liquid crystal display device. Background Art

[0002] In the display field such as liquid crystal displays (LCDs), organic light-emitting diodes (OLEDs), and quantum dots (QDs), colored photosensitive resin compositions are important precursors for the manufacture of color filters. Typically, the colorant in a colored photosensitive resin composition is a pigment containing metal atoms.

[0003] However, during the manufacturing process of color filters and subsequent display devices, some colorant molecules may decompose, releasing metal ions. These released metal ions can accumulate in the polyimide layer or liquid crystal layer, reducing the voltage holding ratio of the display device and causing defects such as image sticking. Therefore, preventing the escape of metal ions and addressing the reduced voltage holding ratio has become an urgent research area during the development of colored photosensitive resin compositions. Summary of the Invention

[0004] The purpose of the present application is to provide an alkali-soluble resin, a colored photosensitive resin composition and a preparation method thereof, a color filter and a liquid crystal display device to solve the above problems.

[0005] To achieve the above objectives, this application adopts the following technical solutions:

[0006] An alkali-soluble resin has the general structural formula:

[0007]

[0008] wherein R1 is any one of an alkyl group having 1 to 5 carbon atoms and an aryl group having 6 to 10 carbon atoms; R2 is any one of an alkyl group having 1 to 5 carbon atoms and an aryl group having 6 to 10 carbon atoms; R3 is any one of an alkyl group having 1 to 4 carbon atoms; and R4 is any one of an alkyl group having 2 to 5 carbon atoms.

[0009] V, W, X, and Y are each independent positive integers.

[0010] Preferably, the alkali-soluble resin has a weight average molecular weight of 8,000-20,000 and an acid value of 60-140 mg·KOH / g.

[0011] The present application also provides a method for preparing the alkali-soluble resin, comprising:

[0012] An alkyl acrylate compound, an alkyl methacrylate compound, an alkenyl isocyanate compound and acrylic acid are reacted to obtain a first polymer;

[0013] The first polymer is reacted with glycidyl methacrylate to obtain a second polymer;

[0014] The second polymer and the lactone compound undergo a third reaction to obtain the alkali-soluble resin;

[0015] The general structural formula of the first polymer is:

[0016]

[0017] The general structural formula of the second polymer is:

[0018]

[0019] The general structural formula of the alkyl acrylate compound is: The general structural formula of the alkyl methacrylate compound is: The general structural formula of the alkenyl isocyanate compound is: The general structural formula of the lactone compound is

[0020] Preferably, the preparation method of the alkali-soluble resin meets one or more of the following conditions:

[0021] (1) The alkyl acrylate compound is selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, tert-pentyl acrylate, cyclopentyl acrylate, benzyl acrylate, and phenylethyl acrylate; preferably tert-butyl acrylate;

[0022] (2) The alkyl methacrylate compound is selected from one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, tert-pentyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, benzyl methacrylate, and phenylethyl methacrylate; preferably benzyl methacrylate;

[0023] (3) The alkenyl isocyanate compound is selected from one or more of 2-isocyanatoethyl methacrylate, 3-isocyanatopropyl methacrylate, and 6-isocyanatohexyl methacrylate; preferably 2-isocyanatoethyl methacrylate;

[0024] (4) The lactone compound is selected from one or more of β-propiolactone, γ-butyrolactone, and δ-caprolactone; preferably β-propiolactone.

[0025] Preferably, the preparation method of the alkali-soluble resin meets one or more of the following conditions:

[0026] (1) The temperature of the first reaction is 65-85°C and the time is 4-10 hours;

[0027] (2) The temperature of the second reaction is 80-100°C and the time is 3-7h;

[0028] (3) The temperature of the third reaction is room temperature and the time is 1-5 hours;

[0029] (4) The raw materials for the first reaction also include an initiator;

[0030] (5) The raw materials for the second reaction further include a polymerization inhibitor and a first catalyst;

[0031] (6) The raw materials for the third reaction also include a second catalyst;

[0032] (7) The first reaction, the second reaction and the third reaction are all carried out under a protective atmosphere.

[0033] The present application also provides a colored photosensitive resin composition, comprising the alkali-soluble resin, a colorant, a photopolymerizable compound, a photopolymerization initiator, and a solvent;

[0034] The amount of the alkali-soluble resin added is 10-65% of the total weight of the solid components in the colored photosensitive resin composition, the amount of the colorant added is 10-70% of the total weight of the solid components in the colored photosensitive resin composition, preferably 20-60% (when the content of the colorant is within the above range, the color concentration of the pixels after the color filter is made is sufficient, and the polymer of the composition can be included in the composition in the required amount to form a clear and complete pattern, which is preferred); the amount of the photopolymerizable compound added is 5-48% of the total weight of the solid components in the colored photosensitive resin composition, the amount of the photopolymerization initiator added is 0.1-4% of the total weight of the solid components in the colored photosensitive resin composition, and the amount of the solvent added is 60-90% of the total weight of the colored photosensitive resin composition.

[0035] In this application, the solid content of the colored photosensitive composition means the total amount of components excluding the solvent.

[0036] Preferably, the colored photosensitive resin composition satisfies one or more of the following conditions:

[0037] (1) The colorant includes dyes and / or pigments; the dyes are selected from one or more of azo dyes, anthraquinone dyes, xanthene dyes, and phthalocyanine dyes; the pigments are selected from organic pigments;

[0038] The azo dye is preferably an azo dye containing a metal complex structure, because the azo dye containing a metal complex structure has better heat resistance and solubility, and can make the color filter have high brightness by increasing the dye content in the red photosensitive resin composition.

[0039] The azo dyes specifically include: CI Solvent Yellow 13, CI Solvent Yellow 19, CI Solvent Yellow 21, CI Solvent Yellow 25, CI Solvent Yellow 25:1, CI Solvent Yellow 81, CI Solvent Yellow 82, CI Solvent Yellow 88, CI Solvent Orange: 40:1, CI Solvent Orange: 41. CI Solvent Orange 62, CI Solvent Orange 81, CI Solvent Orange 99, CI Solvent Orange 83:1, CI Solvent Red 84:1, CI Solvent Red 84:1, CI Solvent Red 90:1, CI Solvent Red 91:1, CI Solvent Red 118, CI Solvent Red 119, CI Solvent Red 112, CI Solvent Red 330, CI Solvent Red 130, etc., but are not limited thereto.

[0040] The anthraquinone dyes include, but are not limited to, Solvent Blue 35, Solvent Blue 45, Solvent Blue 58, Solvent Blue 101, Solvent Blue 122, Solvent Violet 12, Solvent Violet 13, Solvent Violet 26, and Solvent Violet 47.

[0041] The xanthene dye is selected from Acid Red 52, Basic Red 1, Basic Violet 10, Basic Violet 11, Rhodamine B, Rhodamine 6G, Rhodamine 123, and Sulforhodamine B, but is not limited thereto.

[0042] The phthalocyanine compound is selected from phthalocyanine, 2,3-naphthalocyanine, 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine, 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine, 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine, 2,3,9,10,16,17,23,24-octa(octyloxy)-29H,31H-phthalocyanine or 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine, but is not limited thereto.

[0043] Examples of organic pigments include:

[0044] CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments;

[0045] CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;

[0046] CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments;

[0047] CI Pigment Blue 15, 15:3, 15:4, 15:6, 60, 80 and other blue pigments; C.1. Pigment Violet 1, 19, 23, 29, 32, 36-38 and other violet pigments;

[0048] CI Pigment Green 7, 36, 58 and other green pigments.

[0049] (2) The photopolymerizable compound is selected from one or more of trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate or dipentaerythritol hexa(meth)acrylate, and KAYARAD DPHA (Nippon Kayaku); preferably dipentaerythritol hexaacrylate;

[0050] (3) The photopolymerization initiator includes an oxime ester initiator, and the oxime ester initiator is selected from one or more of 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime, 2-[4-(phenylthio)phenyl], 2-(O-benzoyl oxime) and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]hexanone 1-(O-acetyl oxime), Omnirad 1314 (product of BASF), and PBG-345 (product of Trolly);

[0051] (4) The solvent is selected from one or more of aromatic hydrocarbon compounds, ketone compounds, alcohol compounds, ester compounds, and amide compounds; preferably propylene glycol monomethyl ether acetate;

[0052] Preferably, the aromatic hydrocarbon compound is selected from one or more of benzene, toluene, xylene, and mesitylene; the ketone compound is selected from one or more of methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; the alcohol compound is selected from one or more of ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; the ester compound is selected from ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate , 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate and γ-butyrolactone; the amide compound is selected from one or more of N,N-dimethylformamide and N,N-dimethylacetamide;

[0053] (5) The raw materials of the colored photosensitive resin composition further include additives, and the additives include one or more of a surfactant and / or an adhesion promoter;

[0054] Preferably, the surfactant is selected from one or more of F-470, F-475, F-482 and F-554; the adhesion promoter is selected from one or more of vinyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, KBM-403, KBM-503, KBM-803 (commercially available from Shin-Etsu Group);

[0055] Preferably, the additive is added in an amount of 0.1 to 4 weight % of the total weight of the colored photosensitive resin composition.

[0056] Surfactants can be used to improve the coating properties of the photosensitive resin composition.

[0057] The present application also provides a method for preparing the colored photosensitive resin composition, comprising:

[0058] The alkali-soluble resin, the colorant, the photopolymerizable compound, the photopolymerization initiator, and the solvent are mixed.

[0059] The present application also provides a color filter, the raw materials of which include the colored photosensitive resin composition.

[0060] The present application also provides a liquid crystal display device, comprising the color filter.

[0061] Compared with the prior art, the advantages of this application include:

[0062] The alkali-soluble resin provided in the present application contains unsaturated carbon-carbon double bonds, which cross-link with monomers during photocuring to form a dense polymer network, thereby inhibiting the migration of metal ions in pigment particles, and giving the imaging device an excellent voltage holding rate; in addition, it also contains a cyclic structure, which can help improve the mechanical strength of the polymer network structure and its heat resistance; the structure of the alkyl acrylate is used to adjust the viscosity and solubility so that the colored photosensitive resin composition meets the engineering requirements during manufacturing; the amide structure can enhance the alkali solubility of the resin and avoid the generation of residues.

[0063] The color filter prepared by the colored photosensitive resin composition provided in the present application has a voltage holding rate of more than 92%. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following is a brief introduction to the drawings required for use in the embodiments. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope of the present application.

[0065] Figure 1 Actual photos of resins B1 and B2 obtained in the synthesis examples;

[0066] Figure 2 The figures are actual photos of the liquid crystal cells obtained in the examples and comparative examples. DETAILED DESCRIPTION

[0067] The embodiments of the present application will be described in detail below in conjunction with specific examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present application and should not be considered as limiting the scope of the present application. In the examples, if specific conditions are not specified, the conditions are carried out according to conventional conditions or manufacturer recommendations. The reagents or instruments used are not specified by the manufacturer and are conventional products that can be purchased commercially.

[0068] First, the preparation methods of some materials are described as follows:

[0069] 1. The pigment in the colorant is dispersed using a bead mill or the like until the average particle size of the pigment is 0.2 μm or less. Then, a dispersant, dye, ground pigment, and solvent are dissolved and dispersed to obtain a colorant. An alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, a solvent, and additives are added to the colorant dispersion prepared above to produce the colored photosensitive resin composition of the present invention.

[0070] 2. Manufacture of colorants

[0071] 11.0 parts by weight of CI Pigment Green 58 and 2.0 parts by weight of CI Pigment Yellow 150 were used as colorants, 8.0 parts by weight of LPN-6919 (manufactured by BYK) was used as a colorant dispersant, and 79.0 parts by weight of propylene glycol methyl ether acetate was used as a solvent. The mixture was mixed and dispersed in a bead mill for 12 hours to prepare a pigment dispersion composition M1.

[0072] 3. Synthesis of alkali-soluble resin

[0073] (1) An alkyl acrylate compound, an alkyl methacrylate compound, an alkenyl isocyanate compound, and acrylic acid react to obtain a polymer represented by Chemical Formula 2. The reaction formula is as follows:

[0074]

[0075] (2) The polymer shown in Chemical Formula 2 reacts with glycidyl methacrylate to obtain the polymer shown in Chemical Formula 3; the reaction formula is as follows:

[0076]

[0077] (3) The polymer shown in Chemical Formula 3 reacts with lactone to obtain the polymer shown in Chemical Formula 1. The reaction formula is as follows:

[0078]

[0079] Synthesis example 1

[0080] In a four-mouth 1L reactor equipped with a thermometer, a mechanical stirrer, a cooling capacitor and a heating gantry, 200 parts by weight of propylene glycol monomethyl ether acetate, 32 parts by weight of tert-butyl acrylate, 33 parts by weight of benzyl methacrylate, 23 parts by weight of 2-isocyanatoethyl methacrylate, and 12 parts by weight of acrylic acid were added respectively, and the mixture was stirred under a nitrogen atmosphere and the temperature was raised to 70°C. Then, 5 weight% of the total weight of the monomers was added to azobisisobutyronitrile and the reaction was carried out for 6 hours.

[0081] After the reaction is completed and the system cools to room temperature, 23 parts by weight of glycidyl methacrylate, 0.07 weight% of hydroquinone as a polymerization inhibitor relative to the total weight of glycidyl methacrylate, and 0.1 weight% of 2,4,6-tris(dimethylaminomethyl)phenol as a catalyst relative to the total weight of glycidyl methacrylate are added to the reactor, and the temperature is raised to 90° C. and reacted for 5 hours under a nitrogen atmosphere.

[0082] After the second step reaction is completed and the system cools to room temperature, 11 parts by weight of β-propiolactone, 2.5 parts by weight of deionized water, and 0.1% by weight of stannous octoate as a catalyst relative to the total weight of β-propiolactone are added to the reactor, and the mixture is stirred under a nitrogen atmosphere and reacted at room temperature for 2 hours.

[0083] The alkali-soluble resin synthesized above was designated B1. Its weight-average molecular weight (Mw) was 12,200, and its acid value was 83 mg·KOH / g. The weight-average molecular weight was determined by gel permeation chromatography (GPC) in terms of polystyrene. The acid value was determined by acid-base titration.

[0084] Synthesis Example 2 (Comparison)

[0085] In a four-mouth 1L reactor equipped with a thermometer, a mechanical stirrer, a cooling capacitor and a heating gantry, 200 parts by weight of propylene glycol monomethyl ether acetate, 36 parts by weight of tert-butyl acrylate, 37 parts by weight of benzyl methacrylate, and 27 parts by weight of 2-isocyanatoethyl methacrylate were added respectively, and the mixture was stirred under a nitrogen atmosphere and the temperature was raised to 70°C. Then, 5 weight% of the total weight of the monomers was added to azobisisobutyronitrile and the reaction was carried out for 6 hours.

[0086] After the reaction is completed and the system cools to room temperature, 12 parts by weight of β-propiolactone, 2.4 parts by weight of deionized water, and 0.1% by weight of stannous octoate as a catalyst relative to the total weight of β-propiolactone are added to the reactor, and the mixture is stirred under a nitrogen atmosphere and reacted at room temperature for 2 hours.

[0087] The alkali-soluble resin synthesized above was designated as B2, and had a weight average molecular weight (Mw) of 12,000 and an acid value of 85 mg·KOH / g.

[0088] The actual photos of the obtained resins B1 and B2 are as follows Figure 1 shown.

[0089] Next, the preparation of the colored photosensitive resin composition is described as follows:

[0090] Example 1

[0091] A green photosensitive resin composition was prepared by mixing 39 parts by weight of the aforementioned pigment dispersion composition M1, 9.95 parts by weight of the B1 resin produced in Synthesis Example 1, 3.51 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, 0.7 parts by weight of Omnirad 1314 (manufactured by BASF) as a photopolymerization initiator, 0.15 parts by weight of the additive F-554 (manufactured by DIC Corporation of Japan), 0.02 parts by weight of the additive KBM-503M (manufactured by Shin-Etsu Corporation), and 46.67 parts by weight of propylene glycol monomethyl ether acetate.

[0092] Example 2

[0093] A green photosensitive resin composition was prepared by mixing 39 parts by weight of the aforementioned pigment dispersion composition M1, 10.68 parts by weight of the B1 resin produced in Synthesis Example 1, 3.51 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, 0.7 parts by weight of Omnirad 1314 (manufactured by BASF) as a photopolymerization initiator, 0.15 parts by weight of the additive F-554 (manufactured by DIC Corporation of Japan), 0.02 parts by weight of the additive KBM-503M (manufactured by Shin-Etsu Corporation), and 45.94 parts by weight of propylene glycol monomethyl ether acetate.

[0094] Example 3

[0095] A green photosensitive resin composition was prepared by mixing 39 parts by weight of the aforementioned pigment dispersion composition M1, 11.41 parts by weight of the B1 resin prepared in Synthesis Example 1, 3.51 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, 0.7 parts by weight of Omnirad 1314 (manufactured by BASF) as a photopolymerization initiator, 0.15 parts by weight of the additive F-554 (manufactured by DIC Corporation of Japan), 0.02 parts by weight of the additive KBM-503M (manufactured by Shin-Etsu Corporation), and 45.21 parts by weight of propylene glycol monomethyl ether acetate.

[0096] Example 4

[0097] A green photosensitive resin composition was prepared by mixing 39 parts by weight of the aforementioned pigment dispersion composition M1, 9.95 parts by weight of the B1 resin produced in Synthesis Example 1, 3.51 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, 0.7 parts by weight of PBG-345 (Tronly) as a photopolymerization initiator, 0.15 parts by weight of the additive F-554 (DIC Corporation), 0.02 parts by weight of the additive KBM-503M (Shin-Etsu Corporation), and 46.67 parts by weight of propylene glycol monomethyl ether acetate.

[0098] Example 5

[0099] A green photosensitive resin composition was prepared by mixing 39 parts by weight of the aforementioned pigment dispersion composition M1, 10.68 parts by weight of the B1 resin produced in Synthesis Example 1, 3.51 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, 0.7 parts by weight of PBG-345 (Tronly) as a photopolymerization initiator, 0.15 parts by weight of the additive F-554 (DIC Corporation), 0.02 parts by weight of the additive KBM-503M (Shin-Etsu Corporation), and 45.94 parts by weight of propylene glycol monomethyl ether acetate.

[0100] Example 6

[0101] A green photosensitive resin composition was prepared by mixing 39 parts by weight of the aforementioned pigment dispersion composition M1, 11.41 parts by weight of the B1 resin produced in Synthesis Example 1, 3.51 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, 0.7 parts by weight of PBG-345 (Tronly) as a photopolymerization initiator, 0.15 parts by weight of the additive F-554 (DIC Corporation), 0.02 parts by weight of the additive KBM-503M (Shin-Etsu Corporation), and 45.21 parts by weight of propylene glycol monomethyl ether acetate.

[0102] Comparative Example 1

[0103] A green photosensitive resin composition was prepared by mixing 39 parts by weight of the aforementioned pigment dispersion composition M1, 11.41 parts by weight of the B2 resin prepared in Synthesis Example 2, 3.51 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, 0.7 parts by weight of Omnirad 1314 (manufactured by BASF) as a photopolymerization initiator, 0.15 parts by weight of the additive F-554 (manufactured by DIC Corporation of Japan), 0.02 parts by weight of the additive KBM-503M (manufactured by Shin-Etsu Corporation), and 45.21 parts by weight of propylene glycol monomethyl ether acetate.

[0104] Comparative Example 2

[0105] A green photosensitive resin composition was prepared by mixing 39 parts by weight of the aforementioned pigment dispersion composition M1, 11.41 parts by weight of the B2 resin produced in Synthesis Example 2, 3.51 parts by weight of KAYARAD DPHA (Nippon Kayaku) as a photopolymerizable compound, 0.7 parts by weight of PBG-345 (Tronly) as a photopolymerization initiator, 0.15 parts by weight of the additive F-554 (DIC Corporation), 0.02 parts by weight of the additive KBM-503M (Shin-Etsu Corporation), and 45.21 parts by weight of propylene glycol monomethyl ether acetate.

[0106] The voltage holding ratio of the compositions obtained in the examples and comparative examples was evaluated as follows:

[0107] A SiO2 film is formed on the surface to prevent the dissolution of metal ions, and the colored photosensitive resin composition prepared in Examples 1 to 6 and Comparative Examples 1 to 2 is spin-coated on a soda-lime glass substrate on which an ITO (indium-tin oxide alloy) electrode is vapor-deposited in a specified shape, and the coating is performed in such a way that the thickness of the film after drying reaches 2 μm. The substrate with the coating film formed after coating is moved to a reduced pressure drying chamber (VCD), and reduced pressure drying is performed in such a way that the pressure reaches 60 Pa for 22 seconds. After reduced pressure drying, the film is placed in an oven at 100°C for pre-baking for 3 minutes. Then, the entire substrate is produced by full-surface exposure without using a photomask. At this time, a 1KW high-pressure mercury lamp containing all g, h, and i lines is used as the ultraviolet light source, with an ultraviolet radiation intensity of 40 mJ / cm 2The film after ultraviolet irradiation is then immersed in a developer of a KOH aqueous solution with a pH value of 10.5 for 2 minutes. The glass plate coated with the above film is washed with distilled water, blown with nitrogen to dry, and heated in an oven at 230°C for 20 minutes to form a green color filter with a full-surface appearance. After that, the substrate with pixels and the substrate with ITO electrodes vapor-deposited in a specified shape are bonded with a sealant mixed with 1.8mm glass beads, and MLC6608 liquid crystal (manufactured by Merck) is injected to make a liquid crystal cell (the actual photo is as shown in the figure). Figure 2 As shown, 1-6 correspond to Examples 1 to 6 in sequence, and 7 and 8 correspond to Comparative Example 1 and Comparative Example 2 in sequence). Afterwards, the liquid crystal cell is placed in a constant temperature bath at 60°C, and the voltage holding rate of the liquid crystal cell is measured using a liquid crystal voltage holding rate measurement system (VHR-1A, TOYO TECHNICA). The applied voltage at this time is a 5.5V square wave, and the measurement frequency is 60Hz. Here, the voltage holding rate refers to the value obtained by (the liquid crystal cell potential difference after 16.7 milliseconds / the voltage applied at 0 milliseconds). If the voltage holding rate of the liquid crystal cell is less than 90%, it means that the cell cannot maintain the time of 16.7 milliseconds and the applied voltage at the specified level, and the liquid crystal cannot be fully aligned, which may cause phenomena such as afterimages.

[0108] The results are shown in Table 1 below.

[0109] Table 1 Test results

[0110]

[0111] Referring to the results in Table 1, Examples 1 to 6 of the present invention, which contain a photosensitive resin, demonstrate excellent voltage holding ratios. Meanwhile, Comparative Examples 1 and 2, which do not contain a photosensitive resin, demonstrate voltage holding ratios below the specified level.

[0112] From the above results, it can be seen that the colored photosensitive resin composition of the present invention can provide the following effect: it can provide an image developing device with excellent voltage holding ratio.

[0113] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some or all of the technical features therein. These modifications or replacements do not deviate the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.

Claims

1. An alkali-soluble resin, characterized in that Its general structural formula is: wherein R1 is any one of an alkyl group having 1 to 5 carbon atoms and an aryl group having 6 to 10 carbon atoms; R2 is any one of an alkyl group having 1 to 5 carbon atoms and an aryl group having 6 to 10 carbon atoms; R3 is any one of an alkyl group having 1 to 4 carbon atoms; and R4 is any one of an alkyl group having 2 to 5 carbon atoms. V, W, X, and Y are each independent positive integers.

2. The alkali-soluble resin according to claim 1, wherein The alkali-soluble resin has a weight average molecular weight of 8,000-20,000 and an acid value of 60-140 mg·KOH / g.

3. A method for preparing the alkali-soluble resin according to claim 1 or 2, characterized in that: include: An alkyl acrylate compound, an alkyl methacrylate compound, an alkenyl isocyanate compound and acrylic acid are reacted to obtain a first polymer; The first polymer is reacted with glycidyl methacrylate to obtain a second polymer; The second polymer and the lactone compound undergo a third reaction to obtain the alkali-soluble resin; the general structural formula of the first polymer is: The general structural formula of the second polymer is: The general structural formula of the alkyl acrylate compound is: The general structural formula of the alkyl methacrylate compound is: The general structural formula of the alkenyl isocyanate compound is: The general structural formula of the lactone compound is 4. The method for preparing an alkali-soluble resin according to claim 3, wherein One or more of the following conditions are met: (1) The alkyl acrylate compound is selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, tert-pentyl acrylate, cyclopentyl acrylate, benzyl acrylate, and phenylethyl acrylate; preferably tert-butyl acrylate; (2) The alkyl methacrylate compound is selected from one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, tert-pentyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, benzyl methacrylate, and phenylethyl methacrylate; preferably benzyl methacrylate; (3) The alkenyl isocyanate compound is selected from one or more of 2-isocyanatoethyl methacrylate, 3-isocyanatopropyl methacrylate, and 6-isocyanatohexyl methacrylate; preferably 2-isocyanatoethyl methacrylate; (4) The lactone compound is selected from one or more of β-propiolactone, γ-butyrolactone, and δ-caprolactone; preferably β-propiolactone.

5. The method for preparing an alkali-soluble resin according to claim 3, wherein One or more of the following conditions are met: (1) The temperature of the first reaction is 65-85°C and the time is 4-10 hours; (2) The temperature of the second reaction is 80-100°C and the time is 3-7h; (3) The temperature of the third reaction is room temperature and the time is 1-5 hours; (4) The raw materials for the first reaction also include an initiator; (5) The raw materials for the second reaction further include a polymerization inhibitor and a first catalyst; (6) The raw materials for the third reaction also include a second catalyst; (7) The first reaction, the second reaction and the third reaction are all carried out under a protective atmosphere.

6. A colored photosensitive resin composition, characterized in that Comprising the alkali-soluble resin according to claim 1 or 2, a colorant, a photopolymerizable compound, a photopolymerization initiator and a solvent; The amount of the alkali-soluble resin added is 10 to 65% of the total weight of the solid components in the colored photosensitive resin composition, the amount of the colorant added is 10 to 70% of the total weight of the solid components in the colored photosensitive resin composition, the amount of the photopolymerizable compound added is 5 to 48% of the total weight of the solid components in the colored photosensitive resin composition, the amount of the photopolymerization initiator added is 0.1 to 4% of the total weight of the solid components in the colored photosensitive resin composition, and the amount of the solvent added is 60 to 90% of the total weight of the colored photosensitive resin composition.

7. The colored photosensitive resin composition according to claim 6, wherein One or more of the following conditions are met: (1) The colorant includes dyes and / or pigments; the dyes are selected from one or more of azo dyes, anthraquinone dyes, xanthene dyes, and phthalocyanine dyes; the pigments are selected from organic pigments; (2) The photopolymerizable compound is selected from one or more of trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate or dipentaerythritol hexa(meth)acrylate, and KAYARAD DPHA; preferably dipentaerythritol hexaacrylate; (3) The photopolymerization initiator includes an oxime ester initiator, and the oxime ester initiator is selected from one or more of 1,2-octanedione, 1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime, 2-[4-(phenylthio)phenyl], 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]hexanone 1-(O-acetyl oxime), Omnirad 1314, and PBG-345; (4) The solvent is selected from one or more of aromatic hydrocarbon compounds, ketone compounds, alcohol compounds, ester compounds, and amide compounds; preferably propylene glycol monomethyl ether acetate; Preferably, the aromatic hydrocarbon compound is selected from one or more of benzene, toluene, xylene, and mesitylene; the ketone compound is selected from one or more of methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; the alcohol compound is selected from one or more of ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; the ester compound is selected from ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate , 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate and γ-butyrolactone; the amide compound is selected from one or more of N,N-dimethylformamide and N,N-dimethylacetamide; (5) The raw materials of the colored photosensitive resin composition further include additives, and the additives include one or more of a surfactant and / or an adhesion promoter; Preferably, the surfactant is selected from one or more of F-470, F-475, F-482 and F-554; the adhesion promoter is selected from one or more of vinyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, KBM-403, KBM-503 and KBM-803; Preferably, the additive is added in an amount of 0.1 to 2 weight % of the total weight of the colored photosensitive resin composition.

8. A method for preparing the colored photosensitive resin composition according to claim 6 or 7, characterized in that: include: The alkali-soluble resin, the colorant, the photopolymerizable compound, the photopolymerization initiator, and the solvent are mixed.

9. A color filter, characterized in that: The raw materials include the colored photosensitive resin composition according to claim 6 or 7.

10. A liquid crystal display device, characterized in that: The color filter according to claim 9 is included.

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