Sesquiterpene lactone derivatives and their use as anti-cancer agents

Abstract

The application provides a triarylmethane dye containing a silsesquioxane group and an application thereof, and belongs to the technical field of dye compounds. The structure of the triarylmethane dye containing the silsesquioxane group is designed, the silsesquioxane group in the triarylmethane dye can assist in improving the insufficient heat resistance and solvent resistance of the triarylmethane dye, so that the triarylmethane dye containing the silsesquioxane group has excellent comprehensive performance, and further, a dye dispersion liquid and a filter with excellent comprehensive performance are prepared.

Description

Technical Field

[0001] This application belongs to the field of dye compound technology, specifically relating to a triarylmethane dye containing silsesquioxane and its application, and more specifically to a triarylmethane dye containing silsesquioxane, a dye dispersion and a filter. Background Technology

[0002] In recent years, with the development of personal computers, especially portable personal computers, the demand for LCD monitors has increased. The increasing popularity of mobile displays (mobile phones, smartphones, tablet PCs, etc.) has led to a continuously expanding market for LCD monitors. Furthermore, organic light-emitting display devices (such as OLED displays) with high visibility due to their self-emissive nature are also attracting attention as next-generation image display devices. In the performance of these image display devices, improvements in contrast ratio, brightness, and color reproduction are desired, while power consumption is expected to decrease.

[0003] These liquid crystal displays (LCDs) and organic light-emitting diode (OLEDs) primarily achieve color rendering by passing white light from a backlight through color filters, thus displaying color images on the screen. Therefore, the basic performance requirements for color filters include high brightness, high contrast, and high color reproduction. Among the pixel formation methods in color filters, the pigment dispersion method, with its superior characteristics in terms of spectral characteristics, durability, pattern shape, and precision, is the most widely used. By miniaturizing the pigments, the scattering of light transmitted through the color filter caused by the pigment particles is reduced, thereby achieving high brightness and high contrast. However, inorganic pigments have limitations in improving transmittance due to their inherent structure. Furthermore, to achieve high transmittance, the pigments must be highly miniaturized, but miniaturized pigment particles are prone to aggregation, resulting in reduced dispersion stability. In RGB, blue light transmittance is relatively low, and display customers have an increasingly urgent need for improved blue light transmittance; therefore, finding a blue color with high transmittance is crucial.

[0004] Compared to amorphous inorganic pigments with ultra-high transmittance, basic triarylmethane dyes, as cationic dyes, have the following characteristics: relatively bright and deep colors. Furthermore, due to their high transmittance, triarylmethane dyes are used in various applications, including optical materials. However, for color filter applications, the heat resistance and solvent resistance of triarylmethane dyes are insufficient. Therefore, to improve dye fastness, there is an urgent need to provide a novel triarylmethane dye with better heat resistance and solvent resistance. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the purpose of this application is to provide a triarylmethane dye containing silsesquioxane groups and its applications. This application designs the structure of the triarylmethane dye containing silsesquioxane groups, where the silsesquioxane groups help improve the dye's inherent heat resistance and solvent resistance, resulting in superior overall performance. This leads to the preparation of dye dispersions and filters with excellent overall performance.

[0006] To achieve this objective, the following technical solution is adopted in this application:

[0007] In a first aspect, this application provides a triarylmethane dye containing silsesquioxane alkyl groups, wherein the triarylmethane dye containing silsesquioxane alkyl groups has the structure shown in Formula I:

[0008] ;

[0009] R1-R4 each independently represent any one of the following: substituted or unsubstituted C1-C10 straight-chain or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, or substituted or unsubstituted C6-C20 aryl.

[0010] R5-R 13 Each of the following can be independently represented: a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C10 straight-chain or branched alkyl group, or a substituted or unsubstituted C3-C10 cycloalkyl group;

[0011] A represents any one of substituted or unsubstituted C6-C20 arylene or substituted or unsubstituted C3-C20 heteroarylene;

[0012] R1-R 13 The substituents described in A represent independently any one of the following: deuterium atom, halogen atom, cyano group, amino group, hydroxyl group, C1-C10 straight-chain or branched alkyl group, C3-C10 cycloalkyl group, and C6-C10 aryl group;

[0013] POSS stands for sesquioxane alkyl group, with the molecular formula […]. p represents 8, 10, or 12, and POSS is achieved by connecting at least one R with Equation I. Connect, with Equation I Each of the connected R's independently represents any one of the following: a C1-C10 straight-chain or branched alkylene group, a C3-C10 cycloalkylene group, a C2-C10 straight-chain or branched alkenyl group, a C3-C10 cycloalkenyl group, or a C6-C20 aryl group. The remaining R's independently represent any one of the following: a hydrogen atom, a deuterium atom, an amino group, a hydroxyl group, a C1-C10 straight-chain or branched alkyl group, a C3-C10 cycloalkyl group, a C2-C10 straight-chain or branched alkenyl group, a C3-C10 cycloalkenyl group, or a C6-C20 aryl group. Indicates the connection site;

[0014] Z b- PW 12 O 40 3- or PW 11 MoO 40 3- ;

[0015] a represents an integer from 1 to 12;

[0016] m represents an integer from 1 to 40;

[0017] n represents an integer from 1 to 20, and a × m = b × n, where b is 3.

[0018] Organic-inorganic hybrid materials combine the advantages of both organic and inorganic materials, representing a new generation of functional materials following single-component materials, composite materials, and gradient materials. Silsesquioxanes (POSS) possess a hollow, rigid cage-like structure with low density and good gas permeability. They exhibit low dielectric constant, excellent optical properties, heat resistance, flame retardancy, and radiation resistance, making them a novel type of nanostructured organic-inorganic hybrid material that has emerged in recent years. Silsesquioxanes (POSS) rely on an inorganic core composed of an alternating Si-O silicon-oxygen framework. Simultaneously, the substituents R connected to the Si atoms can be inert or reactive organic functional groups, endowing POSS nanoparticles with functionality and high reactivity. This promotes further reactions between POSS and other organic molecules or polymers, forming high-performance organic-inorganic hybrid materials.

[0019] In this application, by introducing a silsesquioxane structure (POSS) into the triarylmethane molecule, the weakness of poor heat resistance and solvent resistance of the chromophore group of triarylmethane dyes is helped to improve. The triarylmethane dye containing silsesquioxane with the specific structure of Formula I can be used as a colorant and further made into a color filter, so that the color filter has high light transmittance and high contrast while ensuring its excellent reliability.

[0020] In this application, C1-C10 can be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10.

[0021] C3-C10 can be C3, C4, C5, C6, C7, C8, C9, or C10.

[0022] C6-C20 can be C6, C8, C10, C12, C13, C15, C18, or C20, etc.

[0023] C3-C20 can be C3, C4, C5, C7, C9, C10, C11, C15, C18, or C20, etc.

[0024] C6-C10 can be C6, C7, C8, C9, or C10.

[0025] C2-C10 can be C2, C3, C4, C5, C6, C7, C8, C9, or C10.

[0026] 'a' represents 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

[0027] m represents 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40, etc.

[0028] n represents 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0029] It should be noted that p indicates that the POSS of 8 is octameric silsesquioxane (T8), whose molecular formula is R8Si8O. 12 The structural formula is This POSS is achieved by at least one R in equation I. (denoted as triarylmethyl alkyl) linkage, The term "linking site" indicates the connection point, and the same applies below. It should be further noted that when 'a' represents 2-6 in compound I, triarylmethane dyes containing sesquioxane groups are mixtures of all isomers with the same molecular formula but different structural formulas, making them difficult to separate. For example, when 'a' represents 2, the linking site of the POSS structure has three possible structures, namely... , , The triarylmethane dyes containing sesquioxane groups are mixtures containing three isomers with the same molecular formula but different specific structural formulas, each with a different POSS linkage site, as shown below:

[0030] , , ;

[0031] Among them, R1-R4, R5-R 13 A, m, Z b- , n has the same definition as above, and the two R′ (i.e. the R in POSS connected to the triarylmethyl group in Formula I) are each independently selected from any one of the following: C1-C10 straight-chain or branched alkylene, C3-C10 cycloalkylene, C2-C10 straight-chain or branched alkenylene, C3-C10 cycloalkenylene, and C6-C20 arylene. The six Rs each independently represent any one of the following: hydrogen atom, deuterium atom, amino group, hydroxyl group, C1-C10 straight-chain or branched alkylene, C3-C10 cycloalkylene, C2-C10 straight-chain or branched alkenylene, C3-C10 cycloalkenylene, and C6-C20 aryl group.

[0032] p indicates that the POSS of 10 is decasilsesquioxane (T10), with the molecular formula R 10 Si 10 O 15 The structural formula is This POSS is linked to a triarylmethane alkyl group in Formula I via at least one R. Similarly, when a in Formula I represents 2-8, triarylmethane dyes containing sesquioxane alkyl groups are a mixture of all isomers with the same molecular formula but different structural formulas, making them difficult to separate.

[0033] p indicates that the POSS of 12 is dodecyl silsesquioxane (T12), with the molecular formula R 12 Si 12 O 18 The structural formula is This POSS is linked to a triarylmethane group in Formula I via at least one R. Similarly, when a in Formula I represents 2-10, triarylmethane dyes containing sesquioxane groups are a mixture of all isomers with the same molecular formula but different structural formulas, making them difficult to separate.

[0034] It should also be noted that the molecular formula is... In silsesquioxane alkyl groups, the specific choices of each R can be the same or different.

[0035] The following are preferred technical solutions of this application, but are not intended to limit the technical solutions provided in this application. The purpose and beneficial effects of this application can be better achieved through the following preferred technical solutions.

[0036] In some specific embodiments, the C1-C10 straight-chain or branched alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, and n-octyl.

[0037] In some specific embodiments, the C3-C10 cycloalkyl group is selected from any one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl.

[0038] In some specific embodiments, the C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl, anthracene, phenanthryl, and fluorenyl.

[0039] In some specific embodiments, the halogen atom is selected from any one of -F, -Cl, -Br, and -I.

[0040] In some specific embodiments, the C6-C10 aryl group is selected from phenyl or naphthyl.

[0041] In some specific embodiments, the straight-chain or branched alkenyl groups of C2-C10 are selected from any one of vinyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, n-pentenyl, and n-hexenyl.

[0042] In some specific embodiments, the cycloalkenyl group of C3-C10 is selected from any one of cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.

[0043] In some specific embodiments, the C6-C20 arylene group is selected from any one of phenylene, naphthylene, biphenylene, anthracene, phenanthrene, and fluorene.

[0044] In some specific embodiments, the C3-C20 heteroaryl group is selected from any one of triazinyl, furanyl, imidazolyl, pyridinyl, dibenzofuranyl, dibenzothiopheneyl, and carbazolyl.

[0045] In some specific embodiments, the straight-chain or branched alkylene groups of C1-C10 are selected from any one of methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, n-pentylene, n-hexylene, and n-octylene.

[0046] In some specific embodiments, the C3-C10 cycloalkyl group is selected from any one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantylene.

[0047] In some specific embodiments, the straight-chain or branched alkenyl groups of C2-C10 are selected from any one of vinylidene, n-propenylidene, isopropenylidene, n-butenylidene, isobutenylidene, n-pentenylidene, and n-hexenylidene.

[0048] In some specific embodiments, the cyclohexene group of C3-C10 is selected from any one of cyclohexene propenyl, cyclohexene butenyl, cyclohexene pentenyl, and cyclohexene.

[0049] In some specific embodiments, R1 and R3 each independently represent any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0050] In some specific embodiments, R2 and R4 each independently represent any one of the following groups, either substituted or unsubstituted: phenyl or naphthyl, wherein the substituted substituent represents any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0051] In some specific embodiments, the R5-R 13 Each can independently represent any one of the following: hydrogen atom, deuterium atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0052] In some specific embodiments, A represents phenylene or naphthylene.

[0053] In some specific embodiments, the triarylmethane dye containing silsesquioxane has the structure shown in Formula I-1:

[0054] ;

[0055] Among them, R1-R4, POSS, Z b- a, m, and n have the same definitions as above.

[0056] In some specific implementations, the POSS represents And at least one R represents any one of methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, cyclopentylene, and cyclohexylene, and the remaining Rs each independently represent any one of hydrogen atom, deuterium atom, amino, hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, and cyclohexyl.

[0057] In some specific implementations, 'a' represents an integer from 1 to 8, such as 1, 2, 3, 4, 5, 6, 7, or 8.

[0058] In some specific implementations, m represents an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0059] In some specific implementations, n represents an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0060] In some specific embodiments, the triarylmethane dye containing silsesquioxane is selected from any one of the following compounds:

[0061] , , , , , , , , , , , , , , , .

[0062] It should be noted that this application does not impose any special limitations on the synthesis method of the above-mentioned triarylmethane dyes containing silsesquioxane groups; commonly used synthesis methods in the art are applicable. The triarylmethane dye containing a silsesquioxane structure as shown in Formula I-1, where R1 and R3 are ethyl, R2 and R4 are o-tolyl, and POSS is... Taking an example where one R is aminopropyl and seven Rs are isopropyl, and where a represents 1, the synthesis method of this triarylmethane dye containing sesquioxane groups includes, but is not limited to, the following steps:

[0063] (1) Preparation of aminopropyl heptaisobutyl cage-like silsesquioxane

[0064] The reaction was prepared by condensation of heptaisobutyltrisilylphenol POSS with 3-aminopropyltriethoxysilane, as shown in the following reaction formula:

[0065] ;

[0066] (2) Synthesis of intermediate A

[0067]

[0068] Intermediate 1 is obtained by reacting aminopropylheptaisobutylcage-like silsesquioxane with 1-iodonaphthalene;

[0069] (3) Synthesis of intermediate 2

[0070]

[0071] Intermediate 2 is obtained by reacting N-ethyl-o-toluidine with dibromobenzophenone.

[0072] (4) Synthesis of intermediate 3

[0073]

[0074] Intermediate 3 is obtained by reacting intermediate 1 and intermediate 2.

[0075] (5) Synthesis of triarylmethane dyes containing sesquioxanes as shown in Formula I-1

[0076]

[0077] Intermediate 3 undergoes anion exchange reaction to obtain a triarylmethane dye containing sesquioxane alkyl groups as shown in Formula I-1.

[0078] It should be noted that the POSS raw materials with a=2-7 used above can be obtained by purchasing them or synthesized using the corner-sealing closed-loop method.

[0079] When a = 2-7 ​​in compound I, the exemplary synthesis methods include, but are not limited to, the following steps:

[0080] (S1) Synthesis of intermediate A (aminated polysilsesquioxane)

[0081]

[0082] The reaction of hydrogen-based silsesquioxanes and allylamines yields intermediate A(R). a Represents a hydrogen atom or , (Indicates the connection site, the same below);

[0083] (S2) Synthesis of intermediate B

[0084]

[0085] Intermediate A reacts with 1-iodonaphthalene to give intermediate B (R b Represents a hydrogen atom or , It is derived from intermediate A in R a express (formed through a reaction)

[0086] (S3) Synthesis of intermediate 2

[0087]

[0088] Intermediate 2 is obtained by reacting N-ethyl-o-toluidine with dibromobenzophenone.

[0089] (S4) Synthesis of intermediate C

[0090]

[0091] Intermediate 2 reacts with intermediate B to yield intermediate C;

[0092] Synthesis of triarylmethane dyes containing sesquioxane alkyl groups as shown in Formula I-1 (S5)

[0093]

[0094] Intermediate C undergoes anion exchange reaction to obtain a triarylmethane dye containing sesquioxane alkyl groups, as shown in Formula I-1.

[0095] It should also be noted that this application does not impose any special restrictions on the specific reaction process parameters (including temperature, time, etc.) in steps (1) to (5) and steps (S1) to (S5) of the preparation method of the compound of formula I provided above. They can be designed according to the actual situation.

[0096] It should be further noted that the molar ratio of hydrogen-based silsesquioxane and allylamine in step (S1) can be adjusted to control the proportion of 'a' in the triaryl methane dyes containing silsesquioxanes shown in Formula I-1. As mentioned earlier, based on the characteristics of the POSS structure, if 'a' in the triaryl methane dyes containing silsesquioxanes shown in Formula I-1 is an integer between 2 and 6, the product obtained in step (S5) is actually an isomer with the same molecular formula but different structural formulas, and cannot be effectively separated. However, this will not affect the effect of improving the dye's reliability. That is, the final triaryl methane dyes containing silsesquioxanes shown in Formula I-1 (where 'a' is an integer between 2 and 6) are actually the sum of isomers with the same molecular formula but different specific structural formulas.

[0097] When a=8, POSS raw materials can be obtained by purchasing or synthesized by hydrolysis-condensation method. Examples of synthesis methods include, but are not limited to, the following steps:

[0098] .

[0099] In a second aspect, this application provides a dye dispersion comprising a triarylmethane dye containing silsesquioxane as described in the first aspect, a dispersion resin, a dispersant, other auxiliaries, and solvent A; the other auxiliaries include phthalic acid; and solvent A includes propylene glycol monomethyl ether acetate and / or diacetone alcohol.

[0100] In some specific embodiments, the dye dispersion comprises the following components in weight percentage: 10-20% of the triarylmethane dye containing silsesquioxane as described in the first aspect, 2-8% of the dispersion resin, 1-5% of the dispersant, 0.5-1.5% of other auxiliaries, and 75-85% of solvent A.

[0101] It should be noted that the amount of dispersing resin used in the dye dispersion is actually the amount of the solid component of the dispersing resin.

[0102] In the dye dispersion, the mass percentage of triarylmethane dyes containing silsesquioxane is 10-20%, for example, it can be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%, etc.

[0103] In the dye dispersion, the mass percentage of the dispersing resin is 2-8%, for example, it can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8%, etc.

[0104] In the dye dispersion, the mass percentage of the dispersant is 1-5%, for example, it can be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%, etc.

[0105] In the dye dispersion, the mass percentage of other auxiliaries is 0.5-1.5%, for example, it can be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4% or 1.5%, etc.

[0106] In the dye dispersion, the mass percentage of solvent A is 75-85%, for example, it can be 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84% or 85%, etc.

[0107] It should be noted that this application does not impose any special restrictions on the specific selection of the dispersing resin, dispersant, other additives, and solvent A. Commonly used dispersing resins, dispersants, other additives, and solvent A in the art are all applicable. The dispersing resin is, by example, including but not limited to: SP-DW-3001 purchased from Showa Chemical Co., Ltd., Japan; the dispersant is, by example, including but not limited to: BYK-LPN-23322 purchased from BAK Chemical Co., Ltd.; the other additives are, by example, including but not limited to: phthalic acid; and the solvents are, by example, including but not limited to: propylene glycol monomethyl ether acetate and diacetone alcohol.

[0108] In some specific embodiments, the preparation method of the dye dispersion includes the following steps: mixing a triarylmethane dye containing silsesquioxane, a dispersion resin, a dispersant, other auxiliaries, solvent A, and zirconia beads with an average particle size of 1.0 mm, and coarsely grinding them for 2-4 h using a paint shaker; then, removing the zirconia beads by filtration, adding zirconia beads with an average particle size of 0.1 mm, and continuing to shake and grind for 10-15 h, removing the zirconia beads by filtration to obtain the dye dispersion.

[0109] Thirdly, the present invention provides a filter comprising a coloring layer, wherein the raw materials for preparing the coloring layer include the dye dispersion as described in the second aspect.

[0110] In some specific embodiments, the coloring layer is prepared from the coloring composition, which includes triarylmethane dyes containing silsesquioxanes as described in the first aspect.

[0111] In some specific embodiments, the coloring composition comprises the following components in parts by weight: 25-35 parts of the dye dispersion as described in the first aspect, 45-60 parts of the alkali-soluble resin, 10-15 parts of the polymerizable monomer, 0.1-0.8 parts of the photoinitiator, 0.1-0.8 parts of the silane coupling agent, 0.01-0.2 parts of the leveling agent, and 30-50 parts of solvent B.

[0112] It should be noted that the amount of alkali-soluble resin used in the coloring composition is actually the amount of the solid component in the dispersion resin.

[0113] In the coloring composition, the weight of the dye dispersion is 25-35 parts, for example, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts or 35 parts, etc.

[0114] In the coloring composition, the alkali-soluble resin is in the amount of 45-60 parts by weight, for example, 45 parts, 46 parts, 48 ​​parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts or 60 parts, etc.

[0115] In the coloring composition, the weight of the polymerizable monomer is 10-15 parts, for example, it can be 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts, 14.5 parts or 15 parts, etc.

[0116] In the coloring composition, the photoinitiator is present in parts by weight of 0.1-0.8, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8 parts.

[0117] In the coloring composition, the silane coupling agent is present in parts by weight of 0.1-0.8, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8.

[0118] In the coloring composition, the leveling agent is present in parts by weight of 0.01-0.2 parts, for example, 0.01 parts, 0.02 parts, 0.04 parts, 0.06 parts, 0.08 parts, 0.1 parts, 0.12 parts, 0.14 parts, 0.16 parts, 0.18 parts, or 0.2 parts, etc.

[0119] In the coloring composition, the solvent B is 30-50 parts by weight, for example, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 ​​parts or 50 parts, etc.

[0120] It should be noted that in this application, there are no special restrictions on the specific selection of alkali-soluble resin, polymerizable monomer, photoinitiator, silane coupling agent, leveling agent and solvent B in the coloring composition. Commonly used alkali-soluble resin, polymerizable monomer, photoinitiator, silane coupling agent, leveling agent and solvent B in the art are all applicable. The alkali-soluble resin, exemplarily including but not limited to, SP-DW-3001 purchased from Showa, Japan; the polymerizable monomer, exemplarily including but not limited to, dipentaerythritol hexaacrylate (DPHA); the photoinitiator, exemplarily including but not limited to, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-O-benzoyl oxime (trade name OXE 01, purchased from BASF); the silane coupling agent, exemplarily including but not limited to, 3-methacryloyloxypropyltrimethoxysilane (KBM503); the leveling agent, exemplarily including but not limited to, EFS-801 purchased from DIC; and the solvent B, exemplarily including but not limited to, propylene glycol methyl ether acetate (PGMEA) and propylene glycol methyl ether (PGME).

[0121] It should be noted that this application does not impose any special limitations on the preparation method of the above-mentioned coloring composition, and commonly used preparation methods in the art are applicable. For example, the preparation method of the coloring composition includes the following steps: using a shaking stirrer to mix the dye dispersion, alkali-soluble resin, polymerizable monomer, photoinitiator, silane coupling agent, leveling agent, and solvent A uniformly to obtain the coloring composition.

[0122] Similarly, this application does not impose any special restrictions on the preparation method of the filter or the thickness of the coloring layer, and the design can be carried out according to the actual situation and actual needs.

[0123] Compared with the prior art, this application has the following beneficial effects:

[0124] (1) This application designs the structure of triarymethane dyes containing silsesquioxane groups. The silsesquioxane groups in the triarymethane dyes can help improve the insufficient heat resistance and solvent resistance of the triarymethane dyes themselves, so that the triarymethane dyes containing silsesquioxane groups have excellent comprehensive performance, and thus a dye dispersion and filter with excellent comprehensive performance are prepared.

[0125] (2) The triarylmethane dyes containing silsesquioxanes provided in this application have high solvent resistance. Under the condition of soaking in NMP at room temperature (25°C) for 6 h, the absorbance of the triarylmethane dyes containing silsesquioxanes provided in this application before and after soaking in N-methylpyrrolidone (NMP) changes. ≤0.005, change in absorbance before and after immersion in dimethylacetamide (DMAC) ≤0.005, change in absorbance before and after immersion in a 0.042 wt% potassium hydroxide solution. ≤0.010; meanwhile, the triarylmethane dyes containing silsesquioxanes provided in this application have good heat resistance, and the temperature at which they lose 5% of their weight, as tested by TGA, is ≥304℃, specifically 304-318℃.

[0126] (3) The triarylmethane dye containing silsesquioxane provided in this application has good dispersion stability in the dye dispersion. The average particle size of the dye dispersion prepared therefrom is 60-68 nm, the initial viscosity is 4.41-5.12 cP, and the viscosity after 30 days of storage at 40℃ and 50%RH is 4.47-5.20 cP, with little viscosity change.

[0127] (4) The filter prepared using the triarylmethane dye containing silsesquioxane provided in this application has high transmittance, high contrast, good heat resistance and solvent resistance, with a BY of 12.99-13.13 and a contrast ratio of 11051-12517. After heat resistance testing, the color difference before and after the filter is... <10, color difference before and after soaking in different solvents (N-methylpyrrolidone, dimethylacetamide, 0.042 wt% potassium hydroxide solution, tetramethylammonium hydroxide) for 30 min. <10. Detailed Implementation

[0128] To facilitate understanding of this application, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of this application.

[0129] The raw materials used in the following examples and comparative examples are all commercially available products. Some of the raw materials are sourced from the following sources: aminopropyl heptaisobutyl cage-like silsesquioxane, purchased from Guangzhou Yixin Technology; 1-iodonaphthalene, purchased from Bide Pharmaceutical; sodium tert-butoxide, purchased from Bide Pharmaceutical; tri-tert-butylphosphine, purchased from Aldrich; palladium acetate, purchased from Leyan Reagent; 12-tungstic phosphate•n-hydrate, purchased from Bide Pharmaceutical; phosphomolybdic tungstate: purchased from PWM-11-1 manufactured by Japan Inorganic Chemical Industry Co., Ltd.; hydrogen-based silsesquioxane, CAS No. 281-50-5; allylamine, CAS No. 107-11-9; octaaminocage-like polysilsesquioxane: purchased from Ruixi Biotechnology, OAPS.

[0130] Example 1

[0131] This embodiment provides a triarylmethane dye 1 containing silsesquioxane and its synthesis method, which is as follows:

[0132] (1) Synthesis of intermediate 1

[0133]

[0134] 20 mmol of aminopropyl heptaisobutylcage silsesquioxane and 22 mmol of 1-iodonaphthalene were added to a reaction flask. 28 mmol of sodium tert-butoxide, 5 mmol of tri-tert-butylphosphine, and 0.2 mmol of palladium acetate were dissolved in 60 mL of xylene. The reaction was carried out at 130-150 °C for 24 h. After the reaction was completed, the mixture was cooled slightly and extracted with pure water. Then, it was dried with magnesium sulfate and concentrated to obtain intermediate 1 (yield 90%).

[0135] (2) Synthesis of intermediate 2

[0136]

[0137] 60 mmol of 4,4'-dibromobenzophenone, 120 mmol of N-ethyl-o-toluidine, 168 mmol of sodium tert-butoxide, and 30 mmol of tri-tert-butylphosphine were dissolved in 200 mL of toluene. Under stirring, after nitrogen purging, 0.6 mmol of palladium acetate was added, and the mixture was refluxed at 100–115 °C for 24 h. After the reaction was completed, water was added after slight cooling, and the mixture was cooled to room temperature. After filtration, the mixture was slurried and refluxed with n-heptane and ethanol (n-heptane to ethanol volume ratio 1:1). After cooling to room temperature, the mixture was filtered to give intermediate 2 (yield 89%).

[0138] (3) Synthesis of intermediate 3

[0139]

[0140] 6 mmol of intermediate 1, 6.1 mmol of intermediate 2, and 50 mL of chlorobenzene were stirred and mixed thoroughly at 50 °C. 24 mmol of phosphorus oxychloride was added dropwise to initiate the reaction, and the mixture was stirred at 50 °C for 24 h. After the reaction was completed, 100 mL of dichloromethane and 100 mL of water were added to dissolve the mixture, and the dichloromethane layer was separated. The dichloromethane layer was washed with pure water until neutral, and then concentrated under reduced pressure at 70 °C until no solvent flowed out, yielding intermediate 3 (yield 85%).

[0141] (4) Synthesis of triarylmethane dye 1 containing sesquioxane

[0142]

[0143] 1.2 mmol of 12-tungstic phosphate•n hydrate was dissolved in 120 mL of a mixed solvent (methanol and water volume ratio of 1:1) to obtain a tungstic phosphate solution. 3 mmol of intermediate 3 was dissolved in 120 mL of methanol to obtain a methanol solution of intermediate 3. Tungstic phosphate solution was added dropwise to the methanol solution of intermediate 3 over 50 min. After the addition was completed, the temperature was raised to 80 °C, and the mixture was refluxed and stirred for 3-5 h. The solid precipitate was filtered out and purified by washing with a methanol-water mixture (volume ratio of 1:2), pure water, and acetone, respectively. After the pH of the filtrate was determined to be neutral, it was dried under reduced pressure to obtain triarylmethane dye 1 containing sesquioxane (yield 90%).

[0144] The purity of triarylmethane dye 1 containing silsesquioxane was analyzed using high-performance liquid chromatography (HPLC). The chromatographic conditions were as follows: Agilent HPLC-1260 system with a UV-Vis detector (VWD), detection wavelength 254 nm, C8 column (4.6 × 150 mm, 3 μm), mobile phase A of acetonitrile, aqueous phase of 0.1 wt% formic acid, column temperature 30 °C, and flow rate 1.0 mL / min. The structure of triarylmethane dye 1 containing silsesquioxane was characterized by mass spectrometry and elemental analysis. The results were: purity 89%; MS (MALDI-TOF MS) (m / z): 1430.97 [M]. + 2861.87 [(WO3)] 12 ·PO3] - ; 13 P NMR (deuterated dimethyl sulfoxide, ppm) δ-15.25; CHNSi elemental analysis (36.19%, 4.53%, 1.79%, 9.38%) confirmed the formation of the target product, a triarylmethane dye containing sesquioxane.

[0145] Example 2

[0146] This embodiment provides a triarylmethane dye 2 containing silsesquioxane and its synthesis method, which is as follows:

[0147] (1) Synthesis of intermediate 4

[0148]

[0149] First, hydrogen-based silsesquioxane, allylamine, and toluene solvent were dried with anhydrous magnesium sulfate for 2 h, and then the desiccant was removed by filtration. 10 mmol of the dried hydrogen-based silsesquioxane was added to 42 g of toluene, and stirred for 30 min at 25 °C, under a nitrogen atmosphere, and at 600 rpm. Then, 21 g of isopropanol solution of chloroplatinic acid (containing 0.21 g of chloroplatinic acid, excluding water) was added, and stirring was continued for 10 min. Then, 20 mmol of dried allylamine was added dropwise at a rate of 1 drop / 3 s using a constant pressure dropping funnel. After the addition was complete, the temperature was raised to 75 °C, and the reaction was continued at a stirring speed of 700 rpm for 7 h. The reaction endpoint was monitored by TLC (disappearance of allylamine spots). After the reaction was completed, the mixture was allowed to stand at 45 °C and 1.5 kPa for 4 h to obtain intermediate 4 (yield 80%).

[0150] (2) Synthesis of intermediate 5

[0151]

[0152] The method for synthesizing intermediate 1 provided in Example 1 is different in that: aminopropyl heptaisobutyl cage-like silsesquioxane is replaced with an equimolar amount of intermediate 4, and the amount of 1-iodonaphthalene is adjusted to 42 mmol, so that the molar ratio of intermediate 4 to 1-iodonaphthalene is 1:2.1, to obtain intermediate 5 (yield 82%).

[0153] (3) Synthesis of intermediate 2

[0154] Intermediate 2 was synthesized according to the synthesis method provided in Example 1;

[0155] (4) Synthesis of intermediate 6

[0156]

[0157] The method for synthesizing intermediate 3 provided in Example 1 is different in that intermediate 1 is replaced with intermediate 5, and the amount of intermediate 2 is adjusted to 12.6 mmol, so that the molar ratio of intermediate 5 to intermediate 2 is 1:2.1, to obtain intermediate 6 (yield of 85%).

[0158] (5) Synthesis of triarylmethane dyes containing sesquioxane groups 2

[0159]

[0160] The method for synthesizing the triarylmethane dye 1 containing silsesquioxane provided in Example 1 is modified by replacing intermediate 3 with an equimolar amount of intermediate 6 and adjusting the amount of 1,2-tungstic phosphate•n-hydrate to 2.6 mmol, so that the molar ratio of intermediate 6 to 1,2-tungstic phosphate•n-hydrate is 1:0.87, thereby obtaining the triarylmethane dye 2 containing silsesquioxane (yield 76%).

[0161] The properties of the triarylmethane dye 2 containing sesquioxane were characterized according to the characterization method provided in Example 1: purity 79%; MS (MALDI-TOF MS) (m / z): 1992.87 [M] + 2861.77 [(WO3)] 12 ·PO3] - ; 13 PNMR (deuterated dimethyl sulfoxide, ppm) δ-15.27; CHNSi elemental analysis (34.58%, 3.75%, 2.17%, 5.81%) confirmed the formation of the target product, a triarylmethane dye containing sesquioxane.

[0162] Example 3

[0163] This embodiment provides a triarylmethane dye 4 containing silsesquioxane and its synthesis method, which is as follows:

[0164] (1) Synthesis of intermediate 7

[0165]

[0166] The preparation method in step (1) of Example 2 is the same, except that the amount of dried allylamine is adjusted to 40 mmol to obtain intermediate 7 (yield of 82%).

[0167] (2) Synthesis of intermediate 8

[0168]

[0169] The synthesis method of intermediate 1 provided in Example 1 is the same, except that: aminopropyl heptaisobutyl cage silsesquioxane is replaced with an equimolar amount of intermediate 7, and the amount of 1-iodonaphthalene is adjusted to 82.6 mmol, so that the molar ratio of intermediate 7 to 1-iodonaphthalene is 1:4.13, to obtain intermediate 8 (yield 85%).

[0170] (3) Synthesis of intermediate 2

[0171] Intermediate 2 was synthesized according to the synthesis method provided in Example 1;

[0172] (4) Synthesis of intermediate 9

[0173]

[0174] The method for synthesizing intermediate 3 provided in Example 1 is the same as that in Example 1, intermediate 1 is replaced with intermediate 8 and the amount of intermediate 2 is adjusted to 24.6 mmol so that the molar ratio of intermediate 8 to intermediate 2 is 1:4.1, and intermediate 9 is obtained (yield 87%).

[0175] (5) Synthesis of triarylmethane dyes containing sesquioxane groups 4

[0176]

[0177] The method for synthesizing the triaryl methane dye 1 containing silsesquioxane provided in Example 1 is modified only by replacing intermediate 3 with an equimolar amount of intermediate 9 and adjusting the amount of 1,2-tungstic phosphate•n-hydrate to 4.6 mmol, so that the molar ratio of intermediate 9 to 1,2-tungstic phosphate•n-hydrate is 1:1.53, thereby obtaining the triaryl methane dye 4 containing silsesquioxane (yield 78%).

[0178] The properties of the triarylmethane dye 4 containing silsesquioxane were characterized using the characterization method provided in Example 1: purity 78%; MS (MALDI-TOF MS) (m / z): 3109.87 [M]. + 2861.81 [(WO3)] 12 ·PO3] - ; 13 PNMR (deuterated dimethyl sulfoxide, ppm) δ-15.29; CHNSi elemental analysis (33.27%, 3.14%, 2.46%, 3.17%) confirmed the formation of the target product, a triarylmethane dye 4 containing sesquioxane.

[0179] Example 4

[0180] This embodiment provides a triarylmethane dye 6 containing silsesquioxane and its synthesis method, which is as follows:

[0181] (1) Synthesis of intermediate 10

[0182]

[0183] The preparation method in step (1) of Example 2 is the same, except that the amount of dried allylamine is adjusted to 60 mmol to obtain intermediate 10 (yield 84%).

[0184] (2) Synthesis of intermediate 11

[0185]

[0186] The synthesis method of intermediate 1 provided in Example 1 is the same, except that: aminopropyl heptaisobutyl cage silsesquioxane is replaced with an equimolar amount of intermediate 10, and the amount of 1-iodonaphthalene is adjusted to 122.6 mmol, so that the molar ratio of intermediate 10 to 1-iodonaphthalene is 1:6.13, to obtain intermediate 11 (yield 86%).

[0187] (3) Synthesis of intermediate 2

[0188] Intermediate 2 was synthesized according to the synthesis method provided in Example 1;

[0189] (4) Synthesis of intermediate 12

[0190]

[0191] The method for synthesizing intermediate 3 provided in Example 1 is different in that intermediate 1 is replaced with intermediate 11, and the amount of intermediate 2 is adjusted to 36.8 mmol, so that the molar ratio of intermediate 11 to intermediate 2 is 1:6.13, to obtain intermediate 12 (yield 83%).

[0192] (5) Synthesis of triarylmethane dyes containing sesquioxane groups 6

[0193]

[0194] The method for synthesizing the triarylmethane dye 1 containing silsesquioxane provided in Example 1 is modified only by replacing intermediate 3 with an equimolar amount of intermediate 12 and adjusting the amount of 12-tungstic phosphate•n-hydrate to 6.7 mmol, so that the molar ratio of intermediate 12 to 12-tungstic phosphate•n-hydrate is 1:2.23, thereby obtaining the triarylmethane dye 6 containing silsesquioxane (yield 78%).

[0195] The properties of the triarylmethane dye 6 containing silsesquioxane were characterized using the characterization method provided in Example 1: purity 77%; MS (MALDI-TOF MS) (m / z): 4227.37 [M] + 2861.63 [(WO3)] 12 ·PO3] - ; 13 PNMR (deuterated dimethyl sulfoxide, ppm) δ-15.28; CHNSi elemental analysis (32.73%, 2.95%, 2.51%, 2.32%) confirmed the formation of the target product, a triarylmethane dye 6 containing sesquioxane.

[0196] Example 5

[0197] This embodiment provides a triarylmethane dye 8 containing silsesquioxane and its synthesis method, which is as follows:

[0198] (1) Synthesis of intermediate 13

[0199]

[0200] The synthesis method of intermediate 1 provided in Example 1 is the same, except that: aminopropyl heptaisobutyl cage-like silsesquioxane is replaced with an equimolar amount of octaamino cage-like polysilsesquioxane, and the amount of 1-iodonaphthalene is adjusted to 162 mmol, so that the molar ratio of octaamino cage-like polysilsesquioxane to 1-iodonaphthalene is 1:8.1, to obtain intermediate 13 (yield 80%).

[0201] (2) Synthesis of intermediate 2

[0202] Intermediate 2 was obtained by referring to the synthesis method of intermediate 2 provided in Example 1;

[0203] (3) Synthesis of intermediate 14

[0204]

[0205] The method for synthesizing intermediate 3 provided in Example 1 is the same as that in Example 1, intermediate 1 is replaced with intermediate 13, and the amount of intermediate 2 is adjusted to 48.6 mmol so that the molar ratio of intermediate 13 to intermediate 2 is 1:8.1, thus obtaining intermediate 14 (yield 78%).

[0206] (4) Synthesis of triarylmethane dyes containing sesquioxane groups 8

[0207]

[0208] The method for synthesizing the triaryl methane dye 1 containing silsesquioxane provided in Example 1 was modified only by replacing intermediate 3 with an equimolar amount of intermediate 14 and adjusting the amount of 1,2-tungstic phosphate•n-hydrate to 8.6 mmol, so that the molar ratio of intermediate 14 to 1,2-tungstic phosphate•n-hydrate was 1:2.87, thus obtaining the triaryl methane dye 8 containing silsesquioxane (yield 83%).

[0209] The properties of the triarylmethane dye 8 containing silsesquioxane were characterized according to the characterization method provided in Example 1: purity 85%; MS (MALDI-TOF MS) (m / z): 5339.91 [M]. + 2861.94 [(WO3)] 12 ·PO3] - ;13 P NMR (deuterated dimethyl sulfoxide, ppm) δ-15.28; CHNSi elemental analysis (32.48%, 2.83%, 2.59%, 1.75%) confirmed the formation of the target product, a triarylmethane dye 8 containing sesquioxane.

[0210] Example 6

[0211] This embodiment provides a triarylmethane dye 9 containing silsesquioxane and its synthesis method, which is as follows:

[0212] Steps (1) to (3) are the same as in Example 1;

[0213] (4) Synthesis of triarylmethane dye 9 containing sesquioxane

[0214]

[0215] The preparation method in step (4) of Example 1 is the same, except that the 12-tungstic phosphate•n hydrate in step (4) is replaced with an equimolar amount of phosphomolybdic acid, and finally a triarylmethane dye 9 containing sesquioxane alkyl groups is obtained (yield 91%).

[0216] The properties of the triarylmethane dye 9 containing silsesquioxane were characterized according to the characterization method provided in Example 1: purity 87%; MS (MALDI-TOF MS) (m / z): 1431.38 [M]. + 2773.52[(WO3)] 11 (MoO3)·PO3] - ; 13 P NMR (deuterated dimethyl sulfoxide, ppm) δ-14.75; Elemental analysis results: CHNSi measured values ​​(36.57%, 4.63%, 1.83%, 9.46%), which confirms the formation of the target product, a triarylmethane dye 9 containing sesquioxane.

[0217] Example 7

[0218] This embodiment provides a triarylmethane dye 10 containing silsesquioxane and its synthesis method, which is as follows:

[0219] Steps (1) to (4) are the same as in Example 2;

[0220] (5) Synthesis of triarylmethane dye 10 containing sesquioxane

[0221]

[0222] The preparation method in step (5) of Example 2 is the same, except that the 12-tungstic phosphate•n hydrate in step (5) is replaced with an equimolar amount of phosphomolybdic acid, and finally a triarylmethane dye 10 containing sesquioxane is obtained (yield 77%).

[0223] The properties of the triarylmethane dye 10 containing silsesquioxane were characterized according to the characterization method provided in Example 1: purity 78%; MS (MALDI-TOF MS) (m / z): 1992.89 [M] + 2773.21 [(WO3)] 11 (MoO3)·PO3] - ; 13 P NMR (deuterated dimethyl sulfoxide, ppm) δ-14.79; CHNSi elemental analysis results (34.58%, 3.75%, 2.17%, 5.81%) confirm the formation of the target product, a triarylmethane dye 10 containing sesquioxane.

[0224] Example 8

[0225] This embodiment provides a triarylmethane dye 12 containing silsesquioxane and its synthesis method, which is as follows:

[0226] Steps (1) to (4) are the same as in Example 3;

[0227] (5) Synthesis of triarylmethane dye 12 containing sesquioxane

[0228]

[0229] The preparation method in step (5) of Example 3 is the same, except that the 12-tungsten phosphate•n hydrate in step (5) is replaced with an equimolar amount of phosphomolybdic acid, and finally a triarylmethane dye 12 containing sesquioxane is obtained (yield 79%).

[0230] The properties of the triarylmethane dye 12 containing silsesquioxane were characterized according to the characterization method provided in Example 1: purity 80%; MS (MALDI-TOF MS) (m / z): 3109.78 [M] + 2773.34 [(WO3)] 11 (MoO3)·PO3] - ; 13 P NMR (deuterated dimethyl sulfoxide, ppm) δ-14.72; CHNSi elemental analysis results (34.35%, 3.27%, 2.52%, 3.26%) confirm the formation of the target product, a triarylmethane dye 12 containing sesquioxane.

[0231] Example 9

[0232] This embodiment provides a triarylmethane dye 14 containing silsesquioxane and its synthesis method, which is as follows:

[0233] Steps (1) to (4) are the same as in Example 4;

[0234] (5) Synthesis of triarylmethane dye 14 containing sesquioxane

[0235]

[0236] The preparation method in step (5) of Example 4 is the same, except that the 12-tungstic phosphate•n hydrate in step (5) is replaced with an equimolar amount of phosphomolybdic acid, and finally a triarylmethane dye 14 containing sesquioxane is obtained (yield 76%).

[0237] The properties of the triarylmethane dye 14 containing silsesquioxane were characterized according to the characterization method provided in Example 1: purity 76%; MS (MALDI-TOF MS) (m / z): 4227.48 [M] + 2773.45 [(WO3)] 11 (MoO3)·PO3] - ; 13 P NMR (deuterated dimethyl sulfoxide, ppm) δ-14.85; CHNSi elemental analysis results (33.32%, 3.17%, 2.67%, 2.28%) confirm the formation of the target product, a triarylmethane dye 14 containing sesquioxane.

[0238] Example 10

[0239] This embodiment provides a triarylmethane dye 16 containing silsesquioxane and its synthesis method, which is as follows:

[0240] Steps (1) to (3) are the same as in Example 1;

[0241] (4) Synthesis of triarylmethane dye 16 containing sesquioxane

[0242]

[0243] The preparation method in step (4) of Example 3 is the same, except that the 12-tungstic phosphate•n hydrate in step (4) is replaced with an equimolar amount of phosphomolybdic acid, and finally a triarylmethane dye 16 containing sesquioxane is obtained (yield 85%).

[0244] The properties of the triarylmethane dye 16 containing silsesquioxane were characterized according to the characterization method provided in Example 1: purity 83%; MS (MALDI-TOF MS) (m / z): 5339.67 [M]. + 2773.39 [(WO3)] 11 (MoO3)·PO3] - ; 13 P NMR (deuterated dimethyl sulfoxide, ppm) δ-14.77; Elemental analysis results: CHNSi measured values ​​(33.35%, 2.94%, 2.63%, 1.82%), which confirms the formation of the target product, a triarylmethane dye 16 containing sesquioxane.

[0245] Comparative Example 1

[0246] This comparative example provides a dye compound purchased from DNP, with the following structure:

[0247] .

[0248] Comparative Example 2

[0249] This comparative example provides a dye compound purchased from Sumitomo Chemical Co., Ltd., with the following structure:

[0250] .

[0251] Comparative Example 3

[0252] This comparative example provides a dye compound purchased from Hodogaya Chemical Co., Ltd., with the following structural formula:

[0253] .

[0254] Comparative Example 4

[0255] This comparative example provides a dye compound, which is intermediate 3 provided in Example 1 above:

[0256] .

[0257] Comparative Example 5

[0258] This comparative example provides a dye compound, which is intermediate 6 provided in Example 2 above:

[0259] .

[0260] Comparative Example 6

[0261] This comparative example provides a dye compound, which is intermediate 14 provided in Example 5 above:

[0262] .

[0263] The properties of the triarylmethane dyes containing silsesquioxanes provided in the above embodiments and the compounds provided in the comparative examples (denoted as dye compounds) were characterized, and the specific characterization methods are as follows:

[0264] Solvent resistance: The dye compounds to be tested were dissolved at equal concentrations (10 ppm) in NMP (N-methylpyrrolidone), DMAC (dimethylacetamide), and 0.042 wt% KOH solutions. Two sets of each dye compound sample were prepared in parallel. One set was directly tested for UV absorbance using a SHIMADZU UV-1900 instrument after dissolution, while the other set was tested for UV absorbance using a SHIMADZU UV-1900 instrument after 6 hours of incubation. The difference in absorbance at 450 nm before and after incubation was recorded and compared. The smaller the difference in absorbance, the better its solvent resistance.

[0265] Heat resistance: The temperature of the dye compound being tested was determined using a “STAR SYSTEM TGA2” manufactured by METTLER TOLEDO (method: heating from room temperature to 500°C at a rate of 10°C / min) and the temperature at which the weight loss was 5% was recorded.

[0266] The performance test data are detailed in Table 1 below.

[0267] Table 1 Performance test results of dye compounds

[0268]

[0269] As can be seen from the above, this application, by designing the structure of the dye compound and further introducing a silsesquioxane structure (POSS) into the triarylmethane dye, obtained a triarylmethane dye containing silsesquioxane alkyl groups with excellent performance, high heat resistance, and solvent resistance.

[0270] The silsesquioxane-containing triarylmethane dyes provided in this application exhibit high solvent resistance. The absorbance changes of the silsesquioxane-containing triarylmethane dyes provided in this application before and after immersion in N-methylpyrrolidone (NMP) at room temperature (25°C) for 6 hours are shown below. ≤0.005, change in absorbance before and after immersion in dimethylacetamide (DMAC) ≤0.005, change in absorbance before and after immersion in a 0.042 wt% potassium hydroxide solution. ≤0.010; meanwhile, the triarylmethane dyes containing silsesquioxanes provided in this application have good heat resistance, and the temperature at which they lose 5% of their weight, as tested by TGA, is ≥304℃, specifically 304-318℃.

[0271] Application Examples 1A-10A, Comparative Application Examples 1A-6A

[0272] Application Examples 1A-10A and Comparative Application Examples 1A-6A each provide a dye dispersion and its preparation method. The dye dispersion comprises the following components in parts by weight: 15 parts dye compound, 4 parts dispersion resin (SP-DW-3001 from Showa, Japan), 3 parts dispersant (BYK-LPN-23322), 1 part other auxiliaries (phthalic acid), 74 parts propylene glycol monomethyl ether acetate, and 4 parts diacetone alcohol. The dye compounds in Application Examples 1A-10A and Comparative Application Examples 1A-6A are, respectively, the triarylmethane dyes containing silsesquioxane provided in Examples 1-10 and the compounds provided in Comparative Examples 1-6. The parts by weight of the dispersion resin refer to the parts by weight of the solid components in the dispersion resin.

[0273] The preparation method of the above dye dispersion is as follows:

[0274] 15 parts of dye compound, 4 parts of dispersion resin (SP-DW-3001 from Showa, Japan), 3 parts of dispersant (BYK-LPN-23322), 1 part of other auxiliaries (phthalic acid), 74 parts of propylene glycol monomethyl ether acetate, 4 parts of diacetone alcohol, and 300 parts by weight of zirconia beads with an average particle size of 1.0 mm were mixed and coarsely ground for 3 h using a paint mixer. Then, the zirconia beads were removed by filtration. After adding zirconia beads with an average particle size of 0.1 mm, the mixture was shaken and ground for another 18 h. The zirconia beads were then removed by filtration to obtain the dye dispersion.

[0275] The dispersion state and stability of the dye dispersions provided in Application Examples 1A-10A and Comparative Application Examples 1A-6A were tested. The specific test methods are as follows:

[0276] Average particle size: The sample was diluted using a dynamic light scattering particle size analyzer with PMA as the dilution solvent to obtain the test sample, and the measurement was performed at 25℃.

[0277] Viscosity: Measured using a Type E viscometer at 60 rpm and 25°C;

[0278] Storage stability: After the dye dispersion to be tested was placed at 40℃ and 50%RH for 30 days, its viscosity was tested using an E-type viscometer at 60 rpm and 25℃.

[0279] The performance test results are detailed in Table 2 below.

[0280] Table 2 Performance test results of dye dispersion

[0281]

[0282] The above results show that the dye dispersion prepared using the silsesquioxane-containing triarylmethane dyes provided in this application as dye compounds exhibits excellent overall performance. Within the same dispersion time, the dye dispersion prepared using the silsesquioxane-containing triarylmethane dyes provided in this application has a smaller average particle size, indicating that the silsesquioxane-containing triarylmethane dyes provided in this application can improve the dispersion efficiency of the dye dispersion. Simultaneously, the dye dispersion provided in this application exhibits excellent dispersion stability, with minimal viscosity change before and after storage.

[0283] The triarylmethane dyes containing silsesquioxanes provided in this application exhibit good dispersion stability in dye dispersions. The dye dispersions prepared in this way have an average particle size of 60-68 nm, an initial viscosity of 4.41-5.12 cP, and a viscosity of 4.47-5.20 cP after 30 days of storage at 40℃ and 50% RH, showing minimal viscosity change.

[0284] Application Examples 1B - 10B, Comparative Application Example 1B, Comparative Application Example 2B, Comparative Application Example 4B, Comparative Application Example 5B

[0285] Application Examples 1B-10B, Comparative Application Example 1B, Comparative Application Example 2B, Comparative Application Example 4B, and Comparative Application Example 5B each provide a filter and a method for preparing the same. The filter comprises a laminated glass substrate (5 cm × 5 cm) and a coloring layer. The coloring layer is prepared from a coloring composition comprising the following components in parts by weight: 28 parts dye dispersion, 52 parts alkali-soluble resin (SP-DW-3001 from Showa, Japan), 12.9 parts polymerizable monomer (dipentaerythritol hexaacrylate, DPHA), and 0.5 parts photoinitiator (1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl oxime, trade name OXE). 01, purchased from BASF), 0.5 parts of silane coupling agent (KBM503), 0.1 parts of leveling agent (purchased from DIC, EFS-801), 39.5 parts of propylene glycol methyl ether acetate (PGMEA), and 11.9 parts of propylene glycol methyl ether (PGME); the dye dispersion in the filters provided in Application Examples 1B-10B and Comparative Application Examples 1B-5B were provided in accordance with Application Examples 1A-10A, Comparative Application Example 1A, Comparative Application Example 2A, Comparative Application Example 4A, and Comparative Application Example 5A; the weight parts of alkali-soluble resin refer to the weight parts of the solid components in the alkali-soluble resin;

[0286] The preparation method of the above-mentioned filter is as follows:

[0287] (1) Mix the components in the coloring composition evenly to obtain the coloring composition coating;

[0288] (2) A coloring composition coating is applied to a glass substrate. First, the substrate is dried under reduced pressure of 30 Pa for 20 s, then pre-baked at 90°C for 2 min to form a pre-baked coating with a thickness of 2.2 μm. The pre-baked coating is then exposed to ultraviolet light at 40 mJ / cm². 2 After the pre-baked coating is irradiated with light, it is developed at 23°C for 60 s using a spray-type developer with a KOH solution of 0.042% by mass. Then, it is rinsed with pure water for 20 s. Finally, it is post-baked at 230°C for 20 min to form a colored layer with a thickness of 2.0 μm on the glass substrate, thus completing the preparation of the filter.

[0289] Comparative Application Example 7B

[0290] This comparative application example provides a filter and its preparation method, which differs from Application Example 1B only in that the dye dispersion provided in Application Example 1A is replaced with an equal weight proportion of B hybrid type dispersion (B156:V-dye is 8:2, purchased from Skata Corporation), and the other conditions are the same as in Application Example 1B.

[0291] The performance of the filters provided in the above application examples and comparative application examples was tested, and the specific test methods are as follows:

[0292] (1) Transmittance: The filters provided in the above application example and the comparative application example were tested using a colorimeter. When the fixed By=0.093, the corresponding BY value can be obtained to evaluate the transmittance of the filter film.

[0293] (2) Contrast ratio: The contrast ratio of the filters provided in the above application example and the comparison application example can be tested using a contrast ratio meter to obtain the contrast ratio value under the corresponding color.

[0294] (3) Heat resistance: The filters provided in the above application examples and comparative application examples were placed in an oven and heated to 230°C. After maintaining the temperature for 2 hours, the colorimetric and transmittance tests were performed again, and the color difference before and after the tests were calculated. , ;

[0295] Judgment criteria: <3, denoted as "AAA"; 3≤ <10, denoted as "AA"; ≥10 is denoted as "X".

[0296] (4) Solvent resistance: The filters provided in the above application examples and comparative application examples were placed in NMP, DMAC, KOH and TMAH (tetramethylammonium hydroxide) solutions respectively, and immersed for 30 min. After that, they were taken out, the color was tested, and the color difference before and after immersion was calculated. , ;

[0297] Judgment criteria: <3, denoted as "AAA"; 3≤ <10, denoted as "AA"; ≥10 is denoted as "X".

[0298] The performance test results are detailed in Tables 3-4 below.

[0299] Table 3. Test results of filter transmittance and contrast.

[0300]

[0301] Table 4. Test results of heat resistance and solvent resistance of the filters

[0302]

[0303] As can be seen from the above, using the triarylmethane dye containing silsesquioxane provided in this application to prepare the coloring layer of the filter results in a filter that simultaneously has high transmittance, high contrast, and good heat resistance and solvent resistance.

[0304] The filters prepared using the triarylmethane dyes containing silsesquioxanes provided in this application exhibit high transmittance, high contrast, good heat resistance, and solvent resistance. Their BY values ​​are 12.99-13.13, and their contrast ratios are 11051-12517. After heat resistance testing, the color difference before and after the filter is [not specified]. <10, color difference before and after soaking in different solvents (N-methylpyrrolidone, dimethylacetamide, 0.042 wt% potassium hydroxide solution, tetramethylammonium hydroxide) for 30 min. <10.

[0305] As can be seen from the comparison of the data of Application Example 4B with Application Example 1B and Application Example 6B in Table 3, the transmittance of the filter provided in Application Example 4B is lower and the contrast is higher than that of the filters provided in Application Example 1B and Application Example 6B. This indicates that the presence of Cl¯ has a slight negative impact on the transmittance of the filter.

[0306] The applicant declares that this application illustrates the detailed process flow through the above embodiments, but this application is not limited to the above detailed process flow, that is, it does not mean that this application must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this application, equivalent substitutions of the raw materials of this application's product, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this application.

Claims

1. A triarylmethane dye containing silsesquioxane, characterized in that, The triarylmethane dye containing silsesquioxane has the structure shown in Formula I: ； R1-R4 each independently represent any one of the following: substituted or unsubstituted C1-C10 straight-chain or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, or substituted or unsubstituted C6-C20 aryl. R5-R 13 Each of the following can be independently represented: a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C10 straight-chain or branched alkyl group, or a substituted or unsubstituted C3-C10 cycloalkyl group; A represents any one of substituted or unsubstituted C6-C20 arylene or substituted or unsubstituted C3-C20 heteroarylene; R1-R 13 The substituents described in A represent independently any one of the following: deuterium atom, halogen atom, cyano group, amino group, hydroxyl group, C1-C10 straight-chain or branched alkyl group, C3-C10 cycloalkyl group, and C6-C10 aryl group; POSS stands for sesquioxane alkyl group, with the molecular formula […]. p represents 8, 10, or 12, and POSS is achieved by connecting at least one R with Equation I. Connect, with Equation I Each of the connected R's independently represents any one of the following: a C1-C10 straight-chain or branched alkylene group, a C3-C10 cycloalkylene group, a C2-C10 straight-chain or branched alkenyl group, a C3-C10 cycloalkenyl group, or a C6-C20 aryl group. The remaining R's independently represent any one of the following: a hydrogen atom, a deuterium atom, an amino group, a hydroxyl group, a C1-C10 straight-chain or branched alkyl group, a C3-C10 cycloalkyl group, a C2-C10 straight-chain or branched alkenyl group, a C3-C10 cycloalkenyl group, or a C6-C20 aryl group. Indicates the connection site; Z b- PW 12 O 40 3- or PW 11 MoO 40 3- ; a represents an integer from 1 to 12; m represents an integer from 1 to 40; n represents an integer from 1 to 20, and a × m = b × n, where b is 3.

2. The triarylmethane dye containing silsesquioxane groups according to claim 1, characterized in that, The C1-C10 straight-chain or branched alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, and n-octyl. The C3-C10 cycloalkyl group is selected from any one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl, anthracene, phenanthryl, and fluorenyl. The halogen atom is selected from any one of -F, -Cl, -Br, and -I; The C6-C10 aryl group is selected from phenyl or naphthyl; The straight-chain or branched alkenyl group of C2-C10 is selected from any one of vinyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, n-pentenyl, and n-hexenyl. The cycloalkenyl group of C3-C10 is selected from any one of cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.

3. The triarylmethane dye containing silsesquioxane groups according to claim 1, characterized in that, The C6-C20 arylene group is selected from any one of phenylene, naphthylene, biphenylene, anthracene, phenanthrene, and fluorene; The C3-C20 heteroaryl group is selected from any one of triazinyl, furanyl, imidazolyl, pyridinyl, dibenzofuranyl, dibenzothiophenyl, and carbazolyl. The C1-C10 straight-chain or branched alkylene groups are selected from any one of methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, n-pentylene, n-hexylene, and n-octylene. The C3-C10 cycloalkyl group is selected from any one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantylene. The straight-chain or branched alkenyl groups of C2-C10 are selected from any one of vinylidene, n-propenylidene, isopropenylidene, n-butenylidene, isobutenylidene, n-pentenylidene, and n-hexenylidene. The C3-C10 cyclohexene group is selected from any one of cyclohexene propenyl, cyclohexene butenyl, cyclohexene pentenyl, and cyclohexene.

4. The triarylmethane dye containing silsesquioxane groups according to claim 1, characterized in that, R1 and R3 each independently represent any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. And / or, R2 and R4 each independently represent any one of the following groups, substituted or unsubstituted: phenyl, naphthyl, wherein the substituted substituent represents any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; And / or, the R5-R 13 Each can independently represent any one of the following: hydrogen atom, deuterium atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. And / or, the A represents phenylene or naphthylene.

5. The triarylmethane dye containing silsesquioxane groups according to claim 1, characterized in that, The triarylmethane dyes containing silsesquioxane groups have the structure shown in Formula I-1: ； Among them, R1-R4, POSS, Z b- a, m, and n have the same definitions as in claim 1.

6. The triarylmethane dye containing silsesquioxane groups according to claim 1, characterized in that, The POSS represents And at least one R represents any one of methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, cyclopentylene, and cyclohexylene, and the remaining Rs each independently represent any one of hydrogen atom, deuterium atom, amino, hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, and cyclohexyl.

7. The triarylmethane dye containing silsesquioxane groups according to claim 1, characterized in that, The 'a' represents an integer from 1 to 8; And / or, where m represents an integer from 1 to 10; And / or, where n represents an integer from 1 to 10.

8. The triarylmethane dye containing silsesquioxane groups according to claim 1, characterized in that, The triarylmethane dyes containing silsesquioxane groups are selected from any one of the following compounds: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 9. A dye dispersion, characterized in that, The dye dispersion comprises a triarylmethane dye containing silsesquioxane as described in any one of claims 1-8, a dispersion resin, a dispersant, other auxiliaries, and solvent A; The other additives include phthalic acid; Solvent A includes propylene glycol monomethyl ether acetate and / or diacetone alcohol.

10. A filter, characterized in that, The filter includes a coloring layer, and the raw materials for preparing the coloring layer include the dye dispersion as described in claim 9.

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