A green display photoresist color paste dimer phthalocyanine dye and a synthesis method thereof

Abstract

The application discloses a kind of green display photoresist color paste with dimer phthalocyanine dye and its synthesis method, the synthesis method includes the following steps: (1) coupling reaction: using phthalic dinitrile and binary alcohol, binary acid or binary ester coupling reaction occurs, after treatment, get bridging intermediate B;(2) cyclization reaction, using zinc salt and bridging intermediate B and functional phthalic dinitrile cyclization reaction occurs, after treatment, get dimer phthalocyanine dye compound C.The application provides a new type of dimer phthalocyanine dye molecule, which can be used for the preparation of green display photoresist color paste, and the heat resistance and light resistance are obviously improved compared with monomolecular dye color paste.In addition, the dimer phthalocyanine dye color paste of the application has high transmittance, high contrast, good dispersibility, color strength and other advantages.

Description

Technical Field

[0001] This invention relates to the field of photoresist color paste technology for displays, specifically to dimer phthalocyanine dyes for green display photoresist color pastes and their synthesis methods. Background Technology

[0002] Color filters are key components in liquid crystal display panels that display color images. These color filter layers are composed of red (R), green (G), and blue (B) colorants made from dyes or pigments. These colorants can convert white backlight into red, green, and blue colors.

[0003] In the field of color filter manufacturing, the traditional pigment dispersion process is widely used in the mass production of liquid crystal displays because it can produce color filters with high durability and excellent color reproduction. However, this process has spectral characteristic defects, such as pigment particle aggregation leading to reduced light transmittance and decreased contrast.

[0004] On the other hand, dye-based color filters, because they can dissolve in the medium and exist in the molecular phase, exhibit lower light scattering, thus achieving higher transmittance and contrast. Applying dyes to color filters is a promising alternative to overcome the limited optical properties of pigments.

[0005] Previous studies have found that color filter materials prepared with dyes have the characteristics of high light transmittance and good color purity. However, due to the insufficient heat resistance, light resistance and solvent resistance of dyes, the dyeing method using dyes as colorants has not been widely used in the production process of commercial color filters. Summary of the Invention

[0006] This study successfully designed and synthesized novel phthalocyanine-based dyes, which possess not only excellent thermal stability but also outstanding spectral properties. Through structural design optimization, we successfully weakened the intermolecular interactions of phthalocyanine molecules, preventing molecular aggregation within the dye. Simultaneously, these dyes exhibit high solubility, dissolving directly in organic solvents. After preparing the synthesized dyes, photoresist dry film devices were simulated by spin-coating them onto glass substrates. Experimental comparisons revealed that the simulated dry film outperformed traditional pigment-based dry films and single-molecule phthalocyanine dye dry film materials in terms of heat resistance, transmittance, and color gamut performance.

[0007] The technical problem to be solved by this invention is to overcome the technical defects of the prior art and to provide a method for synthesizing diphthalocyanine dyes for green display photoresist color pastes. This invention provides a diphthalocyanine dye molecule that can be used in the formulation of green display photoresist color pastes, and its heat resistance and lightfastness are significantly improved compared to monomolecular dye color pastes; furthermore, this diphthalocyanine dye color paste has advantages such as high transmittance, high contrast, good dispersibility, and tinting strength.

[0008] The technical solution adopted by the present invention to solve the above-mentioned technical problems is as follows:

[0009] The chemical structural formula of a phthalocyanine dimer dye for green display photoresist pigment paste is as follows:

[0010]

[0011] The symbols in the formula represent the following meanings:

[0012] R 1 -R 3 Each can independently represent a hydrogen atom, a halogen atom substituent, an alkoxy substituent, or an aryloxy substituent;

[0013] A represents a bridging group, which includes, but is not limited to, any group selected from functional groups containing diols, diacids, or diesters.

[0014] Preferred, R 1 -R 3 Each of the following can be independently represented as a hydrogen atom, a halogen atom substituent, an alkoxy substituent, or an aryloxy substituent; wherein the halogen atom substituent is any one of -F, -Cl, -Br, or -I.

[0015] More preferably, the R 1 Represents any one of the substituents, namely hydrogen atom or halogen atom. More preferably, R 2 and R 3 They are the same alkoxy substituents.

[0016] When the R 2 and R 3 When the group is an alkoxy substituent, the alkoxy substituent is formed by alkyl and alkylene groups linked together by an ether bond, and the end is connected by an oxygen atom.

[0017] Preferably, the R 2 and R 3 When the group is an alkoxy substituent, it is covalently connected to the carbon atom of the benzene ring of the phthalocyanine ring through its terminal oxygen atom. More preferably, the R 2 and R 3The group has the general formula: RO-(CH2)nO-; wherein R is a C1~C6 straight-chain alkyl or branched alkyl, and n is an integer from 2 to 6. More preferably, the R... 2 and R 3 In the general formula, R is selected from any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, and hexyl; n is selected from any one of 2, 3, 4, 5, and 6. More preferably, R... 2 and R 3 It is -OCH2CH2OCH2CH3.

[0018] Preferably, the bridging group is selected from the following substances as the skeletal basis and is derived from the following substances: (1) Diols: ethylene glycol, cyclohexanediol, hydroquinone, biphenyl, naphthol; (2) Dicarboxylic acids: oxalic acid, cyclohexanedicarboxylic acid, phenyl dicarboxylic acid, biphenyl dicarboxylic acid, naphthol; (3) Dicarboxylic acid esters: oxalate, cyclohexanedicarboxylic acid ester, phenyl dicarboxylic acid ester, biphenyl dicarboxylic acid ester, naphthol dicarboxylic acid ester.

[0019] More preferably, the bridging group is: or .

[0020] This invention also provides a method for synthesizing diphthalocyanine dyes for green display photoresist color pastes, comprising the following steps:

[0021] (1) Coupling reaction: using phthalonitrile to undergo a coupling reaction with diol, diacid or diester, and after post-processing, bridging intermediate B is obtained;

[0022] (2) Cycling reaction: Zinc salt reacts with bridging intermediate B and functionalized phthalonitrile to form a cyclization reaction. After post-treatment, dimer phthalocyanine dye compound C is obtained.

[0023] The above synthetic route is as follows:

[0024]

[0025] The symbols in the formula represent the following meanings:

[0026] R 1 -R 3 Each can independently represent a hydrogen atom, a halogen atom substituent, an alkoxy substituent, or an aryloxy substituent;

[0027] A represents a bridging group, primarily a group containing functional groups of diols, diacids, or diesters, such as: ethylene glycol, cyclohexanediol, hydroquinone, biphenyl, naphthol, oxalic acid, cyclohexanedicarboxylic acid, phenylene dicarboxylic acid, biphenyl dicarboxylic acid, naphthalene dicarboxylic acid, oxalate, cyclohexanedicarboxylic acid ester, phenylene dicarboxylic acid ester, biphenyl dicarboxylic acid ester, naphthalene dicarboxylic acid ester, etc. The bridging group includes, but is not limited to, the aforementioned diols, diacids, or diesters.

[0028] Preferably, in step (1), the phthalonitrile is any one or two of 4-nitrophthalonitrile, 4-chlorophthalonitrile, and 4-hydroxyphthalonitrile. More preferably, the phthalonitrile is any one or two of 4-nitrophthalonitrile and 4-chlorophthalonitrile.

[0029] Preferably, in step (1), the molar ratio of the phthalonitrile to the diol, diacid, or diester is 1.5:1 to 5:1. More preferably, the molar ratio of the phthalonitrile to the diol, diacid, or diester in step (1) is 2:1 to 3:1.

[0030] Preferably, in step (1), the base used in the coupling reaction is any one or more of sodium hydride, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate. More preferably, it is any one or more of sodium hydride, lithium tert-butoxide, sodium tert-butoxide, and potassium tert-butoxide.

[0031] Preferably, in step (1), the solvent used in the coupling reaction is any one or more of toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether, methyl cyclopentyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane. More preferably, it is any one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and dimethyl sulfoxide.

[0032] Preferably, in step (1), the reaction temperature of the coupling reaction is 20℃~100℃. More preferably, it is 40℃~80℃.

[0033] Preferably, in step (2), the zinc salt is any one or more of zinc chloride, zinc bromide, zinc iodide, zinc acetate, and zinc trifluoroacetate. More preferably, it is any one or more of zinc iodide and zinc acetate.

[0034] Preferably, in step (2), the functionalized phthalonitrile contains one or more of the following: a halogen atom substituent, an alkoxy substituent, a phenoxy substituent, a mercapto substituent, and a sulfonyl substituent. More preferably, the functionalized phthalonitrile contains one or more of the following: a halogen atom substituent, an alkoxy substituent, and a phenoxy substituent.

[0035] More preferably, in step (2), the functionalized phthalonitrile is selected from any one of 4,5-bis(2-ethoxyethoxy)phthalonitrile, 4,5-bis(2-ethoxyethoxy)-3,6-dichlorophthalonitrile, and 4,5-bis(2-ethoxyethoxy)-3,6-difluorophthalonitrile.

[0036] Preferably, in step (2), the molar ratio of the zinc salt to intermediate B is 3:1 to 1.5:1; more preferably, it is 2:1 to 1.5:1.

[0037] Preferably, in step (2), the solvent for the cyclization reaction is one or more of n-pentanol, benzonitrile, N,N-dimethylformamide, and 1,2-dichlorobenzene; more preferably, the solvent for the cyclization reaction is n-pentanol or benzonitrile.

[0038] Preferably, in step (2), the temperature of the cyclization reaction is 130℃~190℃; more preferably, it is 130℃~170℃.

[0039] Compared with the prior art, the beneficial effects of the present invention are:

[0040] (1) A method for synthesizing a diphthalocyanine dye molecule is provided. The diphthalocyanine dye molecule can be used to prepare a photoresist color paste for green display. The prepared color paste has advantages such as high transmittance, high contrast, good dispersibility, and tinting strength.

[0041] (2) The dimer phthalocyanine dye molecules provided by the present invention have significantly improved heat resistance and light resistance compared with single-molecule dyes. It is speculated that dimer phthalocyanine dyes can consume the absorbed energy through the transfer and torsion of bridging functional groups within the molecule, thereby improving the overall heat resistance and light resistance and solving the problem of poor heat resistance and light resistance of dye-type colorants.

[0042] (3) The synthesis method provided by the present invention has a simple route, readily available commercial reagents, low cost, and can be mass-produced. Attached Figure Description

[0043] Figure 1 The image shows the 1H-NMR spectrum of compound C1 prepared in Example 1 of this invention.

[0044] Figure 2 The image shows the 1H-NMR spectrum of compound C2 prepared in Example 2 of this invention.

[0045] Figure 3 The image shows the 1H-NMR spectrum of compound C3 prepared in Example 3 of this invention.

[0046] Figure 4The image shows the 1H-NMR spectrum of compound C4 prepared in Example 4 of this invention.

[0047] Figure 5 The image shows the 1H-NMR spectrum of compound C5 prepared in Example 5 of this invention.

[0048] Figure 6 The image shows the 1H-NMR spectrum of compound C6 prepared in Example 6 of this invention. Detailed Implementation

[0049] To better understand the content of this invention, further description is provided below with reference to specific embodiments and accompanying drawings. It should be understood that these embodiments are only for further illustration of the invention and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the description of this invention, those skilled in the art may make some non-essential modifications or adjustments to the invention, which still fall within the protection scope of this invention.

[0050] Example 1 (Synthesis of compound C1)

[0051] A method for synthesizing a diphthalocyanine dye for green display photoresist color paste, comprising the following steps:

[0052] (1) Take a dry and clean 500 mL two-necked flask and place a stir bar of appropriate size; add 1,4-cyclohexanediol (23.2 g, 200 mmol, 1.0 eq.) and dry DMF solvent (232 mL); then, under a nitrogen atmosphere and in an ice-water bath, add KO t Bu (53.8 g, 440 mmol, 2.2 eq.); the above reaction system was slowly heated to room temperature, and 4-nitrophthalonitrile (76.2 g, 440 mmol, 1.2 eq.) was added at room temperature; the reaction system was heated to 60 °C and reacted overnight. After the reaction was completed, the mixture was filtered, extracted, and distilled under reduced pressure to obtain the crude product. The crude product was purified by recrystallization to give 62.1 g of bridging intermediate B1, with a yield of 84.3%.

[0053] (2) Take a clean 2000 mL three-necked flask and place a stir bar of appropriate size; add the bridging intermediate B1 (18.4 g, 50 mmol, 1.0 eq.) obtained in the previous step, 4,5-bis(2-ethoxyethoxy)phthalonitrile (100.4 g, 330 mmol, 6.6 eq.), ZnI2 (36.9 g, 100 mmol, 2.0 eq.), and add dry benzonitrile solvent (750 mL). Slowly raise the above reaction system to 160 °C and react overnight; the next day, after the reaction is completed, filter, then distill under reduced pressure and recrystallize to obtain 54.8 g of dark green dimer phthalocyanine dye compound C1 solid, with a yield of 47.1%.

[0054] 1 H NMR (500 MHz, DMSO) δ 9.51 (d, J = 8.1 Hz, 1H), 9.42 (d, J = 2.6Hz, 1H), 9.40 – 9.35 (m, 2H), 8.90 (s, 2H), 8.85 (s, 2H), 8.41 (s, 4H), 7.98(s, 4H), 7.49 (ddd, J = 15.2, 8.1, 2.7 Hz, 2H), 4.51 (p, J = 5.1 Hz, 2H), 4.18 (t, J = 4.9 Hz, 24H), 3.75 (t, J = 5.0 Hz, 24H), 3.54 (q, J = 6.2 Hz, 24H), 2.00 (dd, J = 13.7, 5.0 Hz, 4H), 1.75 (dd, J = 13.7, 5.0 Hz, 4H), 1.21 (t, J = 6.1 Hz, 36H).

[0055] The chemical structural formula of compound C1 is as follows:

[0056] .

[0057] The compound C1 1 See the H-NMR spectrum. Figure 1 .

[0058] Example 2 (Synthesis of compound C2)

[0059] A method for synthesizing a diphthalocyanine dye for green display photoresist color paste, comprising the following steps:

[0060] (1) The bridging intermediate B1 was prepared using the same experimental procedures as in Example 1;

[0061] (2) Compound C2 was prepared using the same experimental procedure as in Example 1, except that 4,5-bis(2-ethoxyethoxy)-3,6-dichlorophthalonitrile (123.2 g, 330 mmol, 6.6 eq.) was used instead of 4,5-bis(2-ethoxyethoxy)phthalonitrile to obtain 59.2 g of dark green dimer phthalocyanine dye compound C2 solid, with a yield of 43.2%.

[0062] 1 H NMR (500 MHz, DMSO) δ 9.51 (d, J = 8.0 Hz, 1H), 9.44 (d, J = 2.7Hz, 1H), 9.41 – 9.36 (m, 2H), 7.49 (ddd, J = 15.2, 8.1, 2.7 Hz, 2H), 4.51 (p,J = 5.1 Hz, 2H), 4.31 (t, J = 4.9 Hz, 24H), 3.76 (t, J = 4.9 Hz, 24H), 3.54(q, J = 6.2 Hz, 24H), 2.00 (dd, J = 13.7, 5.0 Hz, 4H), 1.75 (dd, J = 13.7,5.0 Hz, 4H), 1.21 (t, J = 6.1 Hz, 36H).

[0063] The chemical structural formula of compound C2 is as follows:

[0064] .

[0065] The compound C2 1 See the H-NMR spectrum. Figure 2 .

[0066] Example 3 (Synthesis of compound C3)

[0067] A method for synthesizing a diphthalocyanine dye for green display photoresist color paste, comprising the following steps:

[0068] (1) The bridging intermediate B1 was prepared using the same experimental procedures as in Example 1;

[0069] (2) Compound C3 was prepared using the same experimental procedure as in Example 1, except that 4,5-bis(2-ethoxyethoxy)-3,6-difluorophthalonitrile (112.3 g, 330 mmol, 6.6 eq.) was used instead of 4,5-bis(2-ethoxyethoxy)phthalonitrile to obtain 47.6 g of dark green dimer phthalocyanine dye compound C3 solid, with a yield of 37.5%.

[0070] 1 H NMR (500 MHz, DMSO) δ 9.51 (d, J = 8.0 Hz, 1H), 9.44 (d, J = 2.7Hz, 1H), 9.42 – 9.36 (m, 2H), 7.49 (ddd, J = 15.2, 8.1, 2.7 Hz, 2H), 4.51 (p,J = 5.1 Hz, 2H), 4.30 (t, J = 4.9 Hz, 24H), 3.76 (t, J = 4.9 Hz, 24H), 3.54(q, J = 6.2 Hz, 24H), 2.00 (dd, J = 13.7, 5.0 Hz, 4H), 1.75 (dd, J = 13.7,5.0 Hz, 4H), 1.21 (t, J = 6.1 Hz, 36H).

[0071] The chemical structural formula of compound C3 is as follows:

[0072] .

[0073] The compound C3 1 See the H-NMR spectrum. Figure 3 .

[0074] Example 4 (Synthesis of compound C4)

[0075] A method for synthesizing a diphthalocyanine dye for green display photoresist color paste, comprising the following steps:

[0076] (1) Take a dry and clean 500 mL two-necked flask and place a stir bar of appropriate size; add terephthalic acid (33.2 g, 200 mmol, 1.0 eq.) and dry DMF solvent (332 mL); then, under a nitrogen atmosphere and in an ice-water bath, add sodium hydroxide (17.6 g, 440 mmol, 2.2 eq.); slowly raise the above reaction system to room temperature, and add 4-nitrophthalonitrile (76.2 g, 440 mmol, 1.2 eq.) at room temperature; raise the reaction system to 60 °C and react overnight. After the reaction is complete, filter, extract, and distill under reduced pressure to obtain the crude product. The crude product was purified by recrystallization to obtain 69.7 g of bridging intermediate B2, with a yield of 83.3%;

[0077] (2) Take a clean 2000 mL three-necked flask and place a stir bar of appropriate size; add the bridging intermediate B2 (20.9 g, 50 mmol, 1.0 eq.) obtained in the previous step, 4,5-bis(2-ethoxyethoxy)phthalonitrile (100.4 g, 330 mmol, 6.6 eq.), ZnI2 (36.9 g, 100 mmol, 2.0 eq.), and add dry benzonitrile solvent (800 mL). Slowly raise the above reaction system to 160 °C and react overnight; the next day, after the reaction is completed, filter, then distill under reduced pressure and recrystallize to obtain 49.3 g of dark green dimer phthalocyanine dye compound C4 solid, with a yield of 41.5%.

[0078] 1 H NMR (500 MHz, DMSO) δ 9.68 (d, J = 7.8 Hz, 1H), 9.61 (d, J = 7.8Hz, 1H), 9.59 (d, J = 2.5 Hz, 1H), 9.51 (d, J = 2.7 Hz, 1H), 8.90 (s, 2H),8.85 (s, 2H), 8.41 (s, 4H), 7.97 (d, J = 13.5 Hz, 8H), 7.36 (ddd, J = 13.0,7.9, 2.7 Hz, 2H), 4.18 (t, J = 4.9 Hz, 24H), 3.75 (t, J = 5.0 Hz, 24H), 3.54(q, J = 6.2 Hz, 24H), 1.21 (t, J = 6.1 Hz, 36H).

[0079] The chemical structural formula of compound C4 is as follows:

[0080] .

[0081] The compound C4 1 See the H-NMR spectrum. Figure 4 .

[0082] Example 5 (Synthesis of compound C5)

[0083] A method for synthesizing a diphthalocyanine dye for green display photoresist color paste, comprising the following steps:

[0084] (1) The bridging intermediate B2 was prepared using the same experimental procedures as in Example 4;

[0085] (2) Compound C5 was prepared using the same experimental procedure as in Example 4, except that 4,5-bis(2-ethoxyethoxy)-3,6-dichlorophthalonitrile (123.2 g, 330 mmol, 6.6 eq.) was used instead of 4,5-bis(2-ethoxyethoxy)phthalonitrile to obtain 68.4 g of dark green dimer phthalocyanine dye compound C5 solid, with a yield of 48.7%.

[0086] 1 H NMR (500 MHz, DMSO) δ 9.69 (d, J = 7.8 Hz, 1H), 9.63 (d, J = 7.9Hz, 1H), 9.60 (d, J = 2.7 Hz, 1H), 9.53 (d, J = 2.7 Hz, 1H), 7.96 (s, 4H), 4.31 (t, J = 4.9 Hz, 24H), 3.76 (t, J = 4.9 Hz, 24H), 3.54 (q, J = 6.2 Hz, 24H), 1.21 (t, J = 6.1 Hz, 36H).

[0087] The chemical structural formula of compound C5 is as follows:

[0088] .

[0089] The compound C5 1 See the H-NMR spectrum. Figure 5 .

[0090] Example 6 (Synthesis of compound C6)

[0091] A method for synthesizing a diphthalocyanine dye for green display photoresist color paste, comprising the following steps:

[0092] (1) The bridging intermediate B2 was prepared using the same experimental procedures as in Example 4;

[0093] (2) Compound C6 was prepared using the same experimental procedure as in Example 4, except that 4,5-bis(2-ethoxyethoxy)-3,6-difluorophthalonitrile (112.3 g, 330 mmol, 6.6 eq.) was used instead of 4,5-bis(2-ethoxyethoxy)phthalonitrile to obtain 46.1 g of dark green dimer phthalocyanine dye compound C3 solid, with a yield of 35.6%.

[0094] 1H NMR (500 MHz, DMSO) δ 9.69 (d, J = 7.8 Hz, 1H), 9.63 (d, J = 7.9Hz, 1H), 9.60 (d, J = 2.7 Hz, 1H), 9.53 (d, J = 2.7 Hz, 1H), 7.96 (s, 4H), 7.36 (ddd, J = 13.0, 7.9, 2.7 Hz, 2H), 4.30 (t, J = 4.9 Hz, 24H), 3.76 (t, J= 4.9 Hz, 24H), 3.54 (q, J = 6.2 Hz, 24H), 1.21 (t, J = 6.1 Hz, 36H).

[0095] The chemical structural formula of compound C6 is as follows:

[0096] .

[0097] The compound C6 1 See the H-NMR spectrum. Figure 6 .

[0098] Comparative Example 1 (Synthesis of Compound C7)

[0099] A method for synthesizing a diphthalocyanine dye for green photoresist color paste, comprising the following steps:

[0100] Take a clean 500 mL three-necked flask and place a stir bar of appropriate size; add 4,5-bis(2-ethoxyethoxy)phthalonitrile (30.0 g, 100 mmol, 1.0 eq.), ZnI2 (9.6 g, 30 mmol, 0.3 eq.), and add 300 mL of dry benzonitrile solvent. Slowly raise the above reaction system to 160 °C and react overnight; the next day, after the reaction is completed, filter, then distill under reduced pressure and recrystallize to give 18.6 g of dark green phthalocyanine dye compound C7 solid, with a yield of 58.1%.

[0101] The chemical structural formula of compound C7 is as follows:

[0102] .

[0103] Comparative Example 2 (Synthesis of Compound C8)

[0104] Compound C8 was prepared using the same experimental procedure as in Comparative Example 1, except that 4,5-bis(2-ethoxyethoxy)-3,6-dichlorophthalonitrile (37.3 g, 100 mmol, 1.0 eq.) was used instead of 4,5-bis(2-ethoxyethoxy)phthalonitrile. This yielded 20.2 g of dark green dimer phthalocyanine dye compound C8 solid, with a yield of 51.8%.

[0105] The chemical structural formula of compound C8 is as follows:

[0106] .

[0107] Comparative Example 3 (Synthesis of Compound C9)

[0108] Compound C9 was prepared using the same experimental procedure as in Comparative Example 1, except that 4,5-bis(2-ethoxyethoxy)-3,6-difluorophthalonitrile (34.0 g, 100 mmol, 1.0 eq.) was used instead of 4,5-bis(2-ethoxyethoxy)phthalonitrile. 16.4 g of the dark green dimer phthalocyanine dye compound C9 solid was obtained, with a yield of 45.9%.

[0109] The chemical structural formula of compound C9 is as follows:

[0110] .

[0111] Effect Experiment Example

[0112] Solubility test of dicyanine dye molecules

[0113] The solubility of phthalocyanine dye molecules prepared in Examples 1-6 and Comparative Examples 1-3 in propylene glycol methyl ether acetate (PGMEA) and DMF was tested. A certain amount of dye and organic solvent were weighed, stirred at room temperature for 10 min, and allowed to stand for 24 h. The mixture was filtered three times using a filter membrane, and the filtrate was dried. The solubility S of the dye was calculated.

[0114] S = 100M S / M L

[0115] In the formula, M S This refers to the mass of the dye after drying, in grams (g); in milliliters (M). L This is the mass of the solution, in grams (g).

[0116] The solubility test results of the phthalocyanine dye molecules prepared in Examples 1-6 and Comparative Examples 1-3 are shown in Table 1.

[0117]

[0118] As shown in Table 1, the phthalocyanine dye molecules prepared in Examples 1-6 all have good solubility in PGMEA and DMF.

[0119] II. Thermal stability test of diphthalocyanine dye molecules

[0120] The fabrication of color filters involves a post-baking process at 200℃ or higher, as industrial applications require dye molecules to exhibit good thermal stability at this temperature. Thermogravimetric analysis (TGA) is used to evaluate the thermal stability of synthetic dyes. Under nitrogen protection, the synthetic dyes are heated from room temperature to 500℃ at a rate of 10℃ / min to determine their thermal decomposition temperature T. d .

[0121] The thermal stability test results of the phthalocyanine dye molecules prepared in Examples 1-6 and Comparative Examples 1-3 are shown in Table 2.

[0122]

[0123] As shown in Table 2, the T values ​​of the diphthalocyanine dye molecules prepared in Examples 1-6 are... d Within the temperature range of 277~326℃, the weight loss rate at 230℃ is less than 5%, indicating that the above dye molecules have good thermal stability.

[0124] III. Photostability Test of Dimeric Phthalocyanine Dye Molecules

[0125] The green dye monomer (3%) obtained in each example and comparative example was mixed with resin (Lisennoco Polymer Materials (Shanghai) Co., Ltd., SP-DW-TH3001, 20%), monomer DPHA (5%), photoinitiator TPO (5%), and solvent PMA (67%) to prepare a photoresist. The photoresist was then applied to a 0.4 mm thick glass substrate using a spin coater (800 rpm, 15 s). Subsequently, it was heated and dried on a 150 °C hot plate for 2 minutes. A cured film was obtained by irradiation with 365 nm ultraviolet light for 1 minute. The substrate with the formed colored film was then post-baked in a 230 °C cleanroom oven for 30 minutes to obtain the photoresist colored film. The ∆E(L0,a0,b0) value of the obtained colored film was measured, and the sample was then placed in a 51 W / m² oven. 2 After irradiation at 65 °C for 24 hours under a xenon lamp, the ∆E(L1,a1,b1) value of the obtained colored film was measured again. The color difference was calculated using the International Commission on Illumination (CIE) formula ΔE. ab ={(L1-L0)} 2 +(a1-a0) 2 +(b1-b0) 2} 1 / 2 Calculate color difference, ΔE ab<3 indicates excellent lightfastness.

[0126] The photostability test results of the phthalocyanine dye molecules prepared in Examples 1-6 and Comparative Examples 1-3 are shown in Table 3.

[0127]

[0128] As shown in Table 3, the ΔE values ​​of the diphthalocyanine dye molecules prepared in Examples 1-6 are... ab The values ​​are all less than 3, indicating that the above-mentioned diphthalocyanine dye molecules have good photostability.

[0129] This invention provides a diphthalocyanine dye molecule that can be used in the formulation of photoresist color paste for green displays, and its heat resistance and lightfastness are significantly improved compared to monomolecular dye color paste; in addition, the diphthalocyanine dye color paste has the advantages of high transmittance, high contrast, good dispersibility, and tinting strength.

[0130] The foregoing description is not intended to limit the invention, nor is the invention limited to the examples given. Any changes, modifications, additions, or substitutions made by those skilled in the art within the scope of the invention should also be considered within the protection scope of the invention.

Claims

1. A phthalocyanine dimer dye for green display photoresist pigment paste, characterized in that, The chemical structural formula of the green phthalocyanine dimer dye is as follows: ； The symbols in the formula represent the following meanings: R 1 -R 3 Each can independently represent a hydrogen atom, a halogen atom substituent, an alkoxy substituent, or an aryloxy substituent; A represents a bridging group, which includes, but is not limited to, any group selected from those containing diols, diacids, or diesters.

2. The phthalocyanine dimer dye for green display photoresist color paste as described in claim 1, characterized in that, The bridging group is selected from any of the following bridging groups derived from the skeletal basis: ethylene glycol, cyclohexanediol, hydroquinone, biphenyl, naphthol, oxalic acid, cyclohexanedicarboxylic acid, phenyl dicarboxylic acid, biphenyl dicarboxylic acid, naphthalene dicarboxylic acid, oxalate, cyclohexanedicarboxylic acid ester, phenyl dicarboxylic acid ester, biphenyl dicarboxylic acid ester, and naphthalene dicarboxylic acid ester.

3. The method for synthesizing a diphthalocyanine dye for green display photoresist pigment paste as described in claim 1 or 2, characterized in that, Includes the following steps: (1) Coupling reaction: using phthalonitrile to undergo a coupling reaction with diol, diacid or diester, and after post-processing, bridging intermediate B is obtained; (2) Cycling reaction: Zinc salt reacts with bridging intermediate B and functionalized phthalonitrile to form a cyclization reaction. After post-treatment, dimer phthalocyanine dye compound C is obtained. The above synthetic route is as follows: ； The symbols in the formula represent the following meanings: R 1 -R 3 Each can independently represent a hydrogen atom, a halogen atom substituent, an alkoxy substituent, or an aryloxy substituent; A represents a bridging group, which includes, but is not limited to, any group selected from those containing diol, diacid, or diester functional groups.

4. The method for synthesizing a diphthalocyanine dye for green display photoresist color paste as described in claim 3, characterized in that, In step (1), the phthalonitrile is any one of 4-nitrophthalonitrile, 4-chlorophthalonitrile, and 4-hydroxyphthalonitrile; In step (1), the molar ratio of the phthalonitrile to the diol, diacid or diester is 1.5:1 to 5:1; In step (1), the base used in the coupling reaction is any one or more of sodium hydride, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate. The solvent used in the coupling reaction is any one or more of toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, diethyl ether, methyl tert-butyl ether, methyl cyclopentyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and sulfolane.

5. The method for synthesizing a diphthalocyanine dye for green display photoresist pigment paste as described in claim 3, characterized in that, In step (1), the reaction temperature of the coupling reaction is 20℃~100℃.

6. The method for synthesizing a diphthalocyanine dye for green display photoresist pigment paste as described in claim 3, characterized in that, In step (2), the zinc salt is any one or more of zinc chloride, zinc bromide, zinc iodide, zinc acetate, and zinc trifluoroacetate; In step (2), the molar ratio of the zinc salt to the bridging intermediate B is 3:1 to 1.5:

1.

7. The method for synthesizing a diphthalocyanine dye for green display photoresist pigment paste as described in claim 3, characterized in that, In step (2), the functionalized phthalonitrile contains one or more of the following: halogen substituents, alkoxy substituents, phenoxy substituents, mercapto substituents, and sulfonyl substituents.

8. The method for synthesizing a diphthalocyanine dye for green display photoresist pigment paste as described in claim 3, characterized in that, In step (2), the functionalized phthalonitrile is selected from any one of 4,5-bis(2-ethoxyethoxy)phthalonitrile, 4,5-bis(2-ethoxyethoxy)-3,6-dichlorophthalonitrile, and 4,5-bis(2-ethoxyethoxy)-3,6-difluorophthalonitrile.

9. The method for synthesizing a diphthalocyanine dye for green display photoresist pigment paste as described in claim 3, characterized in that, In step (2), the solvent used in the cyclization reaction is one or more of n-pentanol, benzonitrile, N,N-dimethylformamide, and 1,2-dichlorobenzene.

10. The method for synthesizing a diphthalocyanine dye for green display photoresist pigment paste as described in claim 3, characterized in that, In step (2), the cyclization reaction is carried out at a temperature of 130°C to 190°C.

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