Dye-resin composite, dye-resin composite composition, resin composition, and display panel

Abstract

The embodiment of the invention discloses a dye-resin compound, a dye-resin composite composition, a resin composition and a display panel. The dye-resin compound comprises a resin main body; and, a dye group attached to the resin body; wherein the dye group comprises a phthalocyanine molecule group. After the dye-resin compound, the dye-resin compound composition and the resin composition are prepared into a film layer, the dye is uniformly dispersed in the film layer, and when the film layer is applied to a display device, the display effect is favorably improved; when the coating is applied to preparation of a color film layer, the chromaticity shift before and after high-temperature baking is small, and the quality of the color film is improved.

Description

Technical Field

[0001] This application relates to the field of display technology, specifically to a dye resin composite, a dye resin composite composition, a resin composition, and a display panel. Background Technology

[0002] With the rapid development of display manufacturing technology, the performance requirements for photoresists are increasing, especially in terms of high resolution, high contrast, and color accuracy. As a key material in microelectronics manufacturing, the performance of color photoresists directly affects the quality and performance of the final devices.

[0003] Traditional color photoresists typically use physical dispersion to disperse dyes within a resin matrix. While simple and easy to implement, this method has limitations. Physically dispersed dyes are prone to aggregation or precipitation in the photoresist, which can affect display quality. Furthermore, physically dispersed resins and dyes often exhibit weak interfacial bonding and poor thermal stability, resulting in significant performance degradation after the baking process in film fabrication, thus impacting film quality.

[0004] Therefore, there is an urgent need to develop new materials to solve the above problems. Summary of the Invention

[0005] This application provides a dye resin composite, a dye resin composite composition, a resin composition, and a display panel. When applied to photoresist, the dye resin composite exhibits excellent dispersibility and strong thermal stability, and when subsequently applied to the color filter layer, it enhances the display effect.

[0006] A first aspect of this application provides a dye resin composite, the dye resin composite comprising: Resin body; and, Dye groups attached to the resin matrix; The dye groups include phthalocyanine molecular groups.

[0007] A second aspect of this application provides a dye-resin composite composition comprising a resin and a phthalocyanine dye, wherein the resin has a first group, the phthalocyanine dye has a second group, and the first group and the second group generate a third group under applied conditions.

[0008] A third aspect of this application provides a resin composition comprising the following components by weight percentage: Dye resin: 10%~16%; Monomer: 5-8%; Photoinitiator: 0.2-0.6%; The dye resin includes at least one of the above-mentioned dye resin composites, or the dye resin is prepared from the above-mentioned dye resin composite composition.

[0009] A fourth aspect of this application provides a display panel, the display panel including a color filter layer, the color filter layer being prepared from the above-mentioned dye resin composite, or from the above-mentioned resin composition.

[0010] This application provides a dye-resin composite, a dye-resin composite composition, a resin composition, and a display panel. By linking phthalocyanine dye to the resin substrate through chemical bonds, the dye is uniformly dispersed in the film layer after preparation. When the film layer is applied to a display device, it is beneficial to improve the display effect. Moreover, since the phthalocyanine dye is linked to the resin substrate through chemical bonds, the bonding force is enhanced, resulting in excellent thermal stability. When applied to the preparation of the color filter layer, the color shift before and after high-temperature baking is small, thus improving the quality of the color filter. Attached Figure Description

[0011] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0012] Figure 1 This is a schematic diagram of a display panel provided in an exemplary embodiment of this disclosure; Figure 2 This is another schematic diagram of a display panel provided by an exemplary embodiment of this disclosure.

[0013] Figure 3 This is another schematic diagram of a display panel provided by an exemplary embodiment of the present disclosure.

[0014] Explanation of reference numerals in the attached figures: 100. Display panel; 10. Array substrate; 20. Opposite substrate; 30. Liquid crystal layer; 40. Lower polarizer; 50. Upper polarizer; 60. Color filter layer; 70. Organic light-emitting device; 80. Encapsulation layer; 90. Cover plate. Detailed Implementation

[0015] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0016] This application provides a dye resin composite, a dye resin composite composition, a resin composition, and a display panel 100. These are described in detail below. It should be noted that the order of description of the following embodiments is not intended to limit the preferred order of the embodiments. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc., are used merely as illustrative and do not impose numerical requirements or establish an order. Various embodiments of the present invention may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that a range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any referenced number (fraction or integer) within the indicated range.

[0017] In the embodiments of this application, aromatic groups, aromatic families, and aromatic ring systems have the same meaning and can be used interchangeably.

[0018] In the embodiments of this application, heteroaromatic groups, heteroaromatic families, and heteroaromatic ring systems have the same meaning and can be used interchangeably.

[0019] In the embodiments of this application, "substitution" means that the hydrogen atom in the substituent is replaced by the substituent.

[0020] In the embodiments of this application, when the same substituent appears multiple times, it can be independently selected from different groups. If the general formula contains multiple R, then R can be independently selected from different groups.

[0021] In the embodiments of this application, when the defined group is substituted, it should be understood that the defined group can be substituted by one or more substituents R, wherein R is selected from, but not limited to: deuterium atom, cyano, isocyano, nitro or halogen, alkyl containing 1-20 carbon atoms, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, -NR'R'', silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, halogen Formyl, isocyanate, thiocyanate, isothiocyanate, hydroxyl, trifluoromethyl, and the above groups may be further substituted by substituents acceptable in the art; it is understood that R' and R'' in -NR'R'' are independently selected from, but not limited to: H, deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1-10 carbon atoms, heterocyclic group containing 3-20 ring atoms, aromatic group containing 6-20 ring atoms, and heteroaromatic group containing 5-20 ring atoms. Preferably, R is selected from, but not limited to: deuterium, cyano, isocyano, nitro or halogen, alkyl containing 1-10 carbon atoms, heterocyclic group containing 3-10 ring atoms, aromatic group containing 6-20 ring atoms, heteroaromatic group containing 5-20 ring atoms, silyl, carbonyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, halocarbamoyl, formyl, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl, trifluoromethyl, and the above groups may also be further substituted with substituents acceptable in the art.

[0022] In the embodiments of this application, "ring atom number" refers to the number of atoms in the ring-forming structure of a compound (e.g., monocyclic compound, fused ring compound, cross-linked compound, carbocyclic compound, heterocyclic compound) obtained by atomic bonding. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "ring atom number" described below unless otherwise specified. For example, the benzene ring has 6 ring atoms, the naphthalene ring has 10 ring atoms, and the thiophene group has 5 ring atoms.

[0023] In the embodiments of this application, "aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl. For polycyclic rings, at least one is an aromatic ring system. For example, "substituted or unsubstituted aryl having 6 to 40 ring atoms" refers to an aryl containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl having 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted aryl having 6 to 14 ring atoms, and optionally further substituted on the aryl group; suitable examples include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, fluoranthracene, triphenylene, pyrene, perylene, tetraphenyl, fluorenyl, dinaphthylphenyl, acenaphthyl and their derivatives. It is understandable that multiple aryl groups can also be interrupted by short non-aromatic units (e.g., <10% non-H atoms, such as C, N or O atoms), specifically acenaphthene, fluorene, or 9,9'-diarylfluorene, triarylamine, and diaryl ether systems should also be included in the definition of aryl.

[0024] In the embodiments of this application, "heteroaryl or heteroaromatic group" refers to an aryl group in which at least one carbon atom is replaced by a non-carbon atom, which can be a nitrogen atom, an oxygen atom, a sulfur atom, etc. For example, "substituted or unsubstituted heteroaryl with 5 to 40 ring atoms" refers to a heteroaryl with 5 to 40 ring atoms, preferably a substituted or unsubstituted heteroaryl with 6 to 30 ring atoms, more preferably a substituted or unsubstituted heteroaryl with 6 to 18 ring atoms, and particularly preferably a substituted or unsubstituted heteroaryl with 6 to 14 ring atoms. The heteroaryl may optionally be further substituted, and suitable examples include, but are not limited to, a series of aromatic heterocycles containing nitrogen, oxygen, sulfur, etc., such as pyridine ring, pyran ring, furan ring, thiaran ring, thiophene ring, pyrrole ring, pyrroline ring, imidazole ring, indole ring, quinoline ring, etc. In addition, there are more unique heterocyclic structures such as 1,3-oxazole ring, isoxazole ring, pyrazine ring, pyrimidine ring, pyridazine ring, and 1,3,5-triazine ring, as well as fused aromatic systems such as benzofuran ring, 2-benzofuran ring, benzothiophene ring, and 2-benzothiophene ring. In the examples, we also specifically mentioned various aromatic groups with unique structures and properties, such as 1H-pyrrolidine ring, indole ring, isoindole ring, indene ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinoline ring, benzimidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, porphyrin ring, diazanaphthyl ring, 1,8-naphthidine ring, purine ring, and pteridine ring.

[0025] In the embodiments of this application, "alkyl" can refer to straight-chain, branched, and / or cyclic alkyl groups. The number of carbon atoms in an alkyl group can be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Phrases containing this term, such as "C1-9 alkyl," refer to alkyl groups containing 1 to 9 carbon atoms, and each time it appears, it can independently be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, or C9 alkyl. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3 7-Dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-hepta ...

[0026] In the embodiments of this application, "amine group" refers to an amine derivative having the structural feature of formula -N(X)2, wherein each "X" is independently H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocyclic group, etc. Non-limiting types of amine groups include -NH2, -N(alkyl)2, -NH(alkyl), -N(cycloalkyl)2, -NH(cycloalkyl), -N(heterocyclic)2, -NH(heterocyclic), -N(aryl)2, -NH(aryl), -N(alkyl)(aryl), -N(alkyl)(heterocyclic), -N(cycloalkyl)(heterocyclic), -N(aryl)(heteroaryl), -N(alkyl)(heteroaryl), etc.

[0027] In the embodiments of this application, unless otherwise defined, hydroxyl group refers to -OH, carboxyl group refers to -COOH, carbonyl group refers to -C(=O)-, amino group refers to -NH2, formyl group refers to -C(=O)H, haloformyl group refers to -C(=O)Z (where Z represents halogen), carbamoyl group refers to -C(=O)NH2, isocyanate group refers to -NCO, and isothiocyanate group refers to -NCS.

[0028] In the embodiments of this application, the term "alkoxy" refers to a group with the structure "-O-alkyl", that is, an alkyl group as defined above that is attached to other groups via an oxygen atom. Suitable examples of phrases containing this term include, but are not limited to: methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt), and tert-butoxy (-OC(CH3)3 or -OtBu).

[0029] In the embodiments of this application, the "*" connected to the single bond indicates a connection or fusion site.

[0030] In the embodiments of this application, when no linking site is specified in the group, it means that any linkable site in the group is selected as the linking site.

[0031] In the embodiments of this application, when no fusion site is specified in the group, it means that any fusionable site in the group is selected as the fusion site, and preferably two or more sites in the adjacent position of the group are fusion sites.

[0032] In the embodiments of this application, when the same group contains multiple substituents with the same symbol, the substituents can be the same as or different from each other, for example... The six Rs on the benzene ring can be the same or different from each other.

[0033] In the embodiments of this application, the single bond connecting the substituents extends through the corresponding ring, indicating that the substituent can be connected to any position on the ring, for example... R is attached to any substituted site on the benzene ring; such as express Can be with A fused ring can be formed at any position on the benzene ring.

[0034] The terms cycloalkyl or cycloalkyl as used in this application have the same meaning and are interchangeable.

[0035] In current photoresist manufacturing processes, dye dispersion is often achieved through physical dispersion. Physical dispersion methods suffer from drawbacks such as uneven dispersion and poor thermal stability. When used in the color filter layer 60 of a display panel 100, this type of photoresist can lead to residual development and pattern defects, affecting display quality. Furthermore, traditional photoresist preparation processes are complex, requiring the addition of large amounts of dispersants and coupling agents, increasing process steps and costs. The dispersion process relies on energy-intensive mechanical grinding and ultrasonic treatment, resulting in low production efficiency. During use, this type of photoresist, due to its weak dye binding force, is easily released into the environment, causing pollution.

[0036] To address the aforementioned technical problems, the first aspect of this application provides a dye resin composite, the dye resin composite comprising: Resin body; and, Dye groups attached to the resin matrix; Among them, dye groups include phthalocyanine molecular groups.

[0037] This application provides a dye-resin composite, a dye-resin composite composition, a resin composition, and a display panel. By linking phthalocyanine dye to the resin substrate through chemical bonds, the colorant is uniformly dispersed in the film layer after preparation. When the film layer is applied to a display device, it is beneficial to improve the display effect. Moreover, since the phthalocyanine dye is linked to the resin substrate through chemical bonds, the bonding force is enhanced, resulting in excellent thermal stability. When applied to the preparation of the color filter layer, the color shift before and after high-temperature baking is small, thus improving the quality of the color filter.

[0038] At the same time, by adopting the chemical bonding method between dye and resin, the bonding ability is improved, and the hidden dangers of development residue and pattern defects are eliminated; in the subsequent photoresist preparation process, not only is the dispersion process reduced, but it is also environmentally friendly.

[0039] In some embodiments, the resin body includes at least one resin backbone, the resin backbone includes a plurality of interconnected monomer units, and at least a portion of the monomer units are connected to phthalocyanine molecular groups.

[0040] In some embodiments, the resin body includes at least two resin backbones, and at least a portion of the resin backbones of the at least two resin backbones are connected to the same phthalocyanine molecular group.

[0041] In this embodiment of the application, when the resin body has only one resin main chain, multiple phthalocyanine molecular groups are attached to the resin main chain to form branches, that is, phthalocyanine molecular groups are grafted onto the resin main chain.

[0042] In the embodiments of this application, when the resin body has at least two resin main chains, and at least two resin main chains are simultaneously connected to the same phthalocyanine molecular group, and each phthalocyanine molecular group is simultaneously connected to at least two resin main chains, the dye resin complex has a cross-linked structure.

[0043] In some embodiments, the plurality of monomer units include acrylic acid monomer units; that is, monomer units generated from acrylic acid, for example: ; In some embodiments, the plurality of monomer units further include acrylate monomer units, i.e., monomer units generated from acrylates, for example: .

[0044] In this process, the R' in multiple monomer units may be the same or different, and R' is selected from one or more combinations of aryl, heteroaryl, alkyl, ether, hydroxyl, and alkenyl; the R'' in multiple monomer units may be the same or different, and R'' is selected from one or more combinations of hydrogen atom, alkyl, hydroxyl, carboxyl, epoxy, halogen group, aryl, and heteroaryl; the R''' in multiple monomer units may be the same or different, and R''' is selected from one or more combinations of hydrogen atom, alkyl, hydroxyl, carboxyl, epoxy, halogen group, aryl, and heteroaryl. This indicates the connection site of a single unit.

[0045] In the embodiments of this application, acrylic monomer units and / or acrylic monomer units can be linked to form acrylic resins. Acrylic resins are a better choice for color film layer raw materials due to their high light transmittance, excellent gloss and weather resistance.

[0046] In some embodiments, the dye resin complex further includes a linking group that links the resin matrix and the phthalocyanine molecular group.

[0047] In some embodiments, the linking group is selected from one or more combinations of ester group, amide group, enoyl group, imino group, siloxane group, sulfonate ester, and sulfonamide.

[0048] It is understood that, in the embodiments of this application, the linking groups are not limited to the examples above.

[0049] In some embodiments, the structure of the phthalocyanine molecular group is shown in formula (1):

[0050] Where a is a positive integer greater than or equal to 1 and less than or equal to 16, n is a positive integer greater than or equal to 0 and less than or equal to 15, and a+n is less than or equal to 16, e is a positive integer greater than or equal to 1 and less than or equal to 5, f is a positive integer greater than or equal to 1 and less than or equal to 5, g is a positive integer greater than or equal to 0 and less than or equal to 4, and f+g is a positive integer greater than or equal to 1 and less than or equal to 5; In equation (1), R1 may be the same or different each time it appears, and R1 is selected from hydrogen atoms or halogen atoms; X may be the same or different each time it appears, and X is selected from one or more combinations of ether group, ester group, thioether group, sulfonic acid group, amino group, amide group, and siloxane group; Y may be the same or different each time it appears, and Y is selected from one or more combinations of alkyl, alkenyl, alkynyl, aryl, heteroaryl, halogen group, hydroxyl, carbonyl, aldehyde, ketone, carboxyl, ester, amino, amide, nitro, sulfonic acid, mercapto, cyano, alkoxy, acyl, phosphate, and silanol groups; M is selected from divalent metals; * indicates the connection site with the resin matrix.

[0051] When Y is selected from aryl and / or heteroaryl groups, they can be either compact monocyclic systems or more complex fused-ring systems. Specifically, these aromatic groups encompass classic aromatic systems such as benzene rings, naphthyl rings, anthracene rings, and phenanthrene rings, while also including a series of aromatic heterocycles containing nitrogen, oxygen, sulfur, and other heteroatoms, such as pyridine rings, pyran rings, furan rings, thiaran rings, thiophene rings, pyrrole rings, pyrroline rings, imidazole rings, indole rings, and quinoline rings. In addition, there are more specialized heterocyclic structures such as 1,3-oxazole rings, isoxazole rings, pyrazine rings, pyrimidine rings, pyridazine rings, and 1,3,5-triazine rings, as well as fused aromatic systems such as benzofuran rings, 2-benzofuran rings, benzothiophene rings, and 2-benzothiophene rings. In the examples, we also specifically mentioned a variety of aromatic groups with unique structures and properties, such as 1H-pyrrolidine ring, indole ring, isoindole ring, indene ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinoline ring, benzimidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, porphyrin ring, diazanaphthalene ring, 1,8-naphthidine ring, purine ring, and pteridine ring.

[0052] In some embodiments, a+n is greater than or equal to 4 and less than or equal to 8; for example, the value of a+n is 4, 5, 6, 7, or 8; when a+n is greater than or equal to 4 and less than or equal to 8, it helps to improve the stability of the dye resin complex.

[0053] In some embodiments, at least a portion of R1 in formula (1) is selected from F atoms, and the number of F atoms in formula (1) is 4 to 12, thereby adjusting the wavelength and enhancing solubility when F atoms are introduced onto the phthalocyanine ring. In some preferred embodiments, the number of F atoms is 8.

[0054] In some embodiments, at least a portion of the terminal groups of Y (i.e., the groups in Y that are furthest from the benzene ring) are alkyl groups having 2 to 4 carbon atoms, thereby increasing the compatibility of the dye molecule with the resin matrix and increasing the solubility of the dye-resin complex in the solvent.

[0055] In some embodiments, M is selected from Zn.

[0056] In some embodiments, * indicates a connection site with a linking group.

[0057] In some embodiments, the weight-average molecular weight of the dye resin composite is 10030~11600, for example: 10030, 10050, 10070, 10080, 10800, 10900, 11400, 11600, etc.

[0058] In some embodiments, the acid value of the dye resin complex is 104 to 130, for example, 104, 106, 108, 110, 112, 116, 120, 130, etc.

[0059] This application also provides a dye-resin composite composition comprising a resin and a phthalocyanine dye, wherein the resin has a first group, the phthalocyanine dye has a second group, and the first group and the second group generate a third group under applied conditions.

[0060] It is understood that, in the implementation of this application, the applied conditions are the reaction conditions for the formation of a third group from the first group and the second group, such as heating, stirring, pressure, gas protection, and light irradiation. That is, the conditions applied in this application are selected according to the required reaction conditions for the formation of a third group from the first group and the second group, and are not specifically limited.

[0061] It is understood that in the embodiments of this application, the number of the first group is not specifically limited, and when the resin has multiple first groups, the multiple first groups may be the same or different; the number of the second group is not specifically limited, and when the phthalocyanine dye has multiple second groups, the multiple second groups may be the same or different.

[0062] The dye resin composite composition in this application embodiment is formed by introducing a first group into the resin and a second group into the phthalocyanine dye, and then reacting the two under certain conditions to generate a third group, thereby forming the dye resin composite of the aforementioned embodiment. The third group is a linking group of the dye resin composite (i.e., the dye resin composite of the aforementioned embodiment is prepared from the dye resin composite composition).

[0063] In some embodiments, the resin comprises an acrylic resin, and the molar ratio of the resin to the phthalocyanine dye is 1:(1~1.3), for example: 1:1, 1:1.15, 1:1.2, 1:1.25, 1:1.3, etc.

[0064] In this embodiment, acrylic resins are a better choice for color filter layer raw materials due to their high light transmittance, excellent gloss and weather resistance. At the same time, the carboxyl groups in acrylic resins can be used as the first group to react.

[0065] In some embodiments, the first group includes one or more combinations of hydroxyl, carboxyl, aldehyde, ketone, amino, silanol, sulfonic acid, and acyl chloride groups.

[0066] The second group is selected from one or more combinations of alkyl, alkenyl, alkynyl, aryl, heteroaryl, halogen group, hydroxyl, carbonyl, aldehyde, ketone, carboxyl, ester, amino, amide, nitro, sulfonic acid, mercapto, cyano, alkoxy, acyl, phosphate, and silanol groups.

[0067] The third group is selected from one or more combinations of ester group, amide group, enoyl group, imino group, siloxane group, sulfonate group, and sulfonamide group.

[0068] It is understood that in the embodiments of this application, the first group, the second group, and the third group are not limited to the examples above.

[0069] In some embodiments, when the first group includes an acyl chloride group and / or a carboxyl group, the second group is selected from hydroxyl and / or amino groups. Specifically, when the second group is a hydroxyl group, the third group is an ester group; when the second group is an amino group, the third group is an amide group.

[0070] The inventors of this application discovered that when acrylic resins have the aforementioned first group and phthalocyanine dyes contain the second group, the synthetic route is simple, the conditions are mild and easy to control, and the yield is high, making it easy to produce. In some embodiments, the resin has a weight-average molecular weight of 9200-9600 and an acid value of 80-100.

[0071] In some embodiments, the molecular structure of phthalocyanine dyes is shown in formula (2):

[0072] K may be the same or different each time it appears, and K is selected from one or more combinations of ether group, ester group, thioether group, sulfonic acid group, amino group, amide group, and siloxane group; A may appear the same or different each time it appears. A is selected from one or more combinations of alkyl, alkenyl, alkynyl, aryl, heteroaryl, halogen group, hydroxyl, carbonyl, aldehyde, ketone, carboxyl, ester, amino, amide, nitro, sulfonic acid, mercapto, cyano, alkoxy, acyl, phosphate, and silanol groups. E is selected from divalent metals; b is a positive integer greater than or equal to 1 and less than or equal to 16; h is a positive integer greater than or equal to 1 and less than or equal to 5.

[0073] In equation (2), R2 may be the same or different each time it appears, and R2 is selected from hydrogen atoms or halogen atoms.

[0074] When A is selected from aryl and / or heteroaryl groups, they can be either compact monocyclic systems or more complex fused-ring systems. Specifically, these aromatic groups encompass classic aromatic systems such as benzene rings, naphthyl rings, anthracene rings, and phenanthrene rings, while also including a series of aromatic heterocycles containing nitrogen, oxygen, sulfur, and other heteroatoms, such as pyridine rings, pyran rings, furan rings, thiaran rings, thiophene rings, pyrrole rings, pyrroline rings, imidazole rings, indole rings, and quinoline rings. In addition, there are more specialized heterocyclic structures such as 1,3-oxazole rings, isoxazole rings, pyrazine rings, pyrimidine rings, pyridazine rings, and 1,3,5-triazine rings, as well as fused aromatic systems such as benzofuran rings, 2-benzofuran rings, benzothiophene rings, and 2-benzothiophene rings. In the examples, we also specifically mentioned a variety of aromatic groups with unique structures and properties, such as 1H-pyrrolidine ring, indole ring, isoindole ring, indene ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinoline ring, benzimidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, porphyrin ring, diazanaphthalene ring, 1,8-naphthidine ring, purine ring, and pteridine ring.

[0075] In some embodiments, b is greater than or equal to 4 and less than or equal to 8; for example, the value of b is 4, 5, 6, 7, or 8; when b is greater than or equal to 4 and less than or equal to 8, it helps to improve the stability of the dye resin complex.

[0076] In some embodiments, at least a portion of R2 in formula (2) is selected from F atoms, and the number of F atoms in formula (1) is 4 to 12, thereby adjusting the wavelength and enhancing solubility when F atoms are introduced onto the phthalocyanine ring. In some preferred embodiments, the number of F atoms is 8.

[0077] In some embodiments, at least a portion of the terminal group of A in formula (2) (i.e. the group in Y that is away from the benzene ring) is an alkyl group with 2 to 4 carbon atoms. For example, A is selected from n-butoxycarbonyl, propoxycarbonyl, ethoxycarbonyl, etc., thereby increasing the compatibility between the dye molecule and the resin matrix and increasing the solubility of the dye resin complex in the solvent.

[0078] In some embodiments, at least a portion of A in formula (2) has a second group, such as hydroxyl, amino, etc., and in this case, A with at least a portion of the second group forms a linking group in the dye resin complex with the first group in the resin.

[0079] It is understood that in the embodiments of this application, b = a + n.

[0080] In some embodiments, E is selected from Zn.

[0081] In some embodiments, the phthalocyanine dye is selected from at least one of the following compounds: .

[0082] In the above chemical formula, n-Bu represents n-butyl, Et represents ethyl, Me represents methyl, and Pr represents propyl.

[0083] In some embodiments, the dye-resin composite composition further includes a catalyst for catalyzing the reaction between the first group and the second group to generate a third group.

[0084] In some embodiments, the molar ratio of catalyst to phthalocyanine dye is (0.8~1.3):1.

[0085] In some embodiments, the dye-resin composite composition further includes a condensing agent used in a condensation reaction to generate the third group from the first group and the second group.

[0086] In some embodiments, the molar ratio of condensing agent to phthalocyanine dye is (0.8~1.3):1.

[0087] In some specific embodiments, the catalyst includes, for example, triethylamine, and the condensing agent includes at least one of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide salt, and 1-hydroxybenzotriazole.

[0088] In the embodiments of this application, the first group is selected from acyl chloride group and / or carboxyl group, and the second group is selected from amino group and / or hydroxyl group.

[0089] The phthalocyanine dye used in this application is prepared by the following method: Synthesis of the intermediate: Phthalonil derivative I, potassium fluoride, and N,N-dimethylformamide (DMF) were mixed and cooled on ice. Then, a solution of compound II in a certain proportion was added, and the mixture was stirred as is for 5-16 hours (the temperature can be increased after slow addition). After the reaction was complete, the reaction solution was filtered and concentrated. The precipitate was separated by filtration and purified by column chromatography to obtain the intermediate.

[0090]

[0091] Where c is a positive integer greater than or equal to 1 and less than or equal to 4; The phthalonitrile process is used as the key route for the preparation of metal phthalocyanines. This process not only greatly simplifies the production process but also helps to improve production efficiency and reduce costs. Of particular note is the considerable yield achieved by this synthetic route. Due to the mild and easily controlled reaction conditions, and the careful optimization of each reaction step, the formation of byproducts can be minimized, ensuring high purity and high yield of the target product.

[0092] In some embodiments, compound II comprises at least one derivative of hydroxybenzene. Further, in some embodiments, compound II comprises at least one ester derivative of p-hydroxyphenol, p-hydroxyaniline, or p-hydroxybenzoic acid.

[0093] The intermediate, metal iodide EI2, and DMF were mixed and reacted. After the reaction was complete, the reaction solution was cooled and poured into ethanol. The resulting solid component was washed with ethanol, dried under reduced pressure, and passed through a column to obtain the dye. Dye molecules can be synthesized sequentially using different intermediates.

[0094]

[0095] This application describes phthalocyanine dyes A to H, and methods for preparing phthalocyanine dyes A to H: <Synthesis Example 1: Synthesis of Dye A> 4.00 g (20 mmol) tetrafluorophthalonitrile, 2.90 g (5.0 mmol) potassium fluoride, and 25 mL N,N-dimethylformamide were mixed, and the mixture was then cooled in an ice bath. Next, a solution of 2.20 g (20 mmol) p-hydroxyphenol dissolved in 25 mL N,N-dimethylformamide was slowly added dropwise. The mixture was stirred continuously for 5 hours while maintaining the original temperature. After the reaction was complete, the reaction solution was filtered, concentrated, and dried, and intermediate 1 was obtained by column chromatography with a mass of 4.81 g (yield: 82%). This purity data was calculated based on the area percentage of the target component in the high-performance liquid chromatography analysis.

[0096]

[0097] 4.81 g (16.6 mmol) of intermediate 1 and 1.59 g (4.98 mmol) of zinc iodide were mixed thoroughly with 20 mL of N,N-dimethylformamide (DMF), and then heated at 150 °C for 10–12 hours. After the reaction was complete, the reaction system was allowed to cool naturally to room temperature and carefully transferred to 20 mL of ethanol to induce precipitation of the solid product. The solid was collected by filtration and washed repeatedly with ethanol to remove impurities, followed by drying under reduced pressure at 40 °C to remove residual solvent. Finally, 4.38 g of the target dye A (yield: 86%, purity: 98.0%) was successfully obtained by column chromatography purification. Based on the results of H-NMR and MALDI-MS, dye A was confirmed to contain the following compounds:

[0098] 1H NMR (DMSO-d6, ppm) δ: 9.29(s, 4H), 6.75(d, 8H), 6.69(d, 8H). [M] = 1224.11, measured M = 1224.13 <Synthesis Example 2: Synthesis of Dye B> 4.00 g (20 mmol) tetrafluorophthalonitrile, 2.90 g (5.0 mmol) potassium fluoride, and 25 mL N,N-dimethylformamide were mixed and then cooled in an ice bath. Next, a solution of 2.18 g (20 mmol) p-hydroxyaniline dissolved in 25 mL N,N-dimethylformamide was slowly added dropwise. The mixture was stirred continuously for 8 hours while maintaining the original temperature. After the reaction was complete, the reaction solution was filtered, concentrated, and dried, and intermediate B was obtained by column chromatography with a mass of 4.51 g (yield: 78%). This purity data was calculated based on the area percentage of the target component in the high-performance liquid chromatography analysis.

[0099]

[0100] 4.51 g (15.6 mmol) of intermediate 2 and 1.49 g (4.68 mmol) of zinc iodide were mixed thoroughly with 20 mL of N,N-dimethylformamide (DMF), and then heated at 150 °C for 10–12 hours. After the reaction was complete, the reaction system was allowed to cool naturally to room temperature and carefully transferred to 20 mL of ethanol to induce precipitation of the solid product. The solid was collected by filtration and washed repeatedly with ethanol to remove impurities, followed by drying under reduced pressure at 40 °C to remove residual solvent. Finally, 3.86 g of the target dye B (yield: 78%, purity: 98.0%) was successfully obtained by column chromatography purification. Based on the results of H-NMR and MALDI-MS, the following compounds were confirmed to be present in dye B:

[0101] 1H NMR (DMSO-d6, ppm) δ: 8.41(s, 8H), 6.67(d, 8H), 6.42(d, 8H). [M / z]=1220.11, measured M=1220.12 <Synthesis Example 3: Synthesis of Dye C> 4.00 g (20 mmol) tetrafluorophthalonitrile, 5.8 g (10.0 mmol) potassium fluoride, and 25 mL N,N-dimethylformamide were mixed and then cooled in an ice bath. Next, a solution of 4.40 g (40 mmol) p-hydroxyphenol dissolved in 25 mL N,N-dimethylformamide was slowly added dropwise. The mixture was stirred continuously for 7 hours while maintaining the original temperature. After the reaction was complete, the reaction solution was filtered, concentrated, and dried, and intermediate 3 was obtained by column chromatography with a mass of 6.57 g (yield: 86%). This purity data was calculated based on the area percentage of the target component in the high-performance liquid chromatography analysis.

[0102]

[0103] 6.57 g (17.2 mmol) of intermediate 3 and 3.29 g (10.32 mmol) of zinc iodide were mixed thoroughly with 20 mL of N,N-dimethylformamide (DMF), and then heated at 150 °C for 11 hours. After the reaction was complete, the reaction system was allowed to cool naturally to room temperature and carefully transferred to 20 mL of ethanol to induce precipitation of the solid product. The obtained solid was collected by filtration and washed repeatedly with ethanol to remove impurities, followed by drying under reduced pressure at 40 °C to remove residual solvent. Finally, 5.87 g of the target dye C (yield: 86%, purity: 98.0%) was successfully obtained by column chromatography purification. According to the results of H-NMR and MALDI-MS, dye C was confirmed to contain the following compounds:

[0104] 1H NMR (DMSO-d6, ppm) δ: 9.31(s, 4H), 6.75(d, 8H), 6.69(d, 8H). [M / z] = 1584.17, measured M = 1584.19 <Synthesis Example 4: Synthesis of Dye D> 4.00 g (20 mmol) tetrafluorophthalonitrile, 5.8 g (10.0 mmol) potassium fluoride, and 25 mL N,N-dimethylformamide were mixed and then cooled in an ice bath. Next, a solution of 4.36 g (40 mmol) p-hydroxyaniline dissolved in 25 mL N,N-dimethylformamide was slowly added dropwise. The mixture was stirred continuously for 6 hours while maintaining the original temperature. After the reaction was complete, the reaction solution was filtered, concentrated, and dried, and intermediate 4 was obtained by column chromatography with a mass of 5.70 g (yield: 75%). This purity data was calculated based on the area percentage of the target component in the high-performance liquid chromatography analysis.

[0105]

[0106] 5.7 g (15.0 mmol) of intermediate C, 2.87 g (9.0 mmol) of zinc iodide, and 20 mL of N,N-dimethylformamide (DMF) were mixed thoroughly and then heated at 150 °C for 13 hours. After the reaction was complete, the reaction system was allowed to cool naturally to room temperature and carefully transferred to 20 mL of ethanol to induce precipitation of the solid product. The solid was collected by filtration and washed repeatedly with ethanol to remove impurities. Residual solvent was then removed by vacuum drying at 40 °C. Finally, 4.79 g of the target dye D (yield: 81%, purity: 98.0%) was successfully obtained by column chromatography purification. The following compounds were confirmed to be present in dye D based on H-NMR and MALDI-MS results.

[0107]

[0108] 1H NMR (DMSO-d6, ppm) δ: 8.44(s, 8H), 6.67(d, 8H), 6.42(d, 8H). [M / z]=1576.30, measured M=1576.32 <Synthesis Example 5: Synthesis of Dye E> 4.00 g (20 mmol) tetrafluorophthalonitrile, 5.8 g (10.0 mmol) potassium fluoride, and 25 mL N,N-dimethylformamide were mixed and then cooled in an ice bath. Next, a solution of 2.2 g (20 mmol) p-hydroxyphenol and 3.32 g (20 mmol) ethyl p-hydroxybenzoate dissolved in 25 mL N,N-dimethylformamide was slowly added dropwise. The mixture was stirred continuously for 11 hours while maintaining the original temperature. After the reaction was complete, the reaction solution was filtered, concentrated, and dried, and intermediate 5 was obtained by column chromatography with a mass of 7.18 g (yield: 82%). This purity data was calculated based on the area percentage of the target component in the high-performance liquid chromatography analysis.

[0109]

[0110] 7.18 g (16.4 mmol) of intermediate 5 and 3.14 g (9.8 mmol) of zinc iodide were mixed thoroughly with 20 mL of N,N-dimethylformamide (DMF), and then heated at 150 °C for 11 hours. After the reaction was complete, the reaction system was allowed to cool naturally to room temperature and carefully transferred to 20 mL of ethanol to induce precipitation of the solid product. The obtained solid was collected by filtration and washed repeatedly with ethanol to remove impurities, followed by drying under reduced pressure at 40 °C to remove residual solvent. Finally, 5.79 g of the target dye E (yield: 78%, purity: 97.0%) was successfully obtained by column chromatography purification. The following compounds were confirmed to be present in dye E based on the results of H-NMR and MALDI-MS.

[0111]

[0112] 1H NMR (DMSO-d6, ppm) δ:9.28(s, 4H), 7.93(d, 8H), 7.03(d, 8H), 6.75(d, 8H), 6.69 (d, 8H), 4.29(m, 8H), 1.44(t, 12H). [M / z]=1809.28, measured M=1809.31 <Synthesis Example 6: Synthesis of Dye F> 4.00 g (20 mmol) tetrafluorophthalonitrile, 5.8 g (10.0 mmol) potassium fluoride, and 25 mL N,N-dimethylformamide were mixed, and the mixture was then cooled in an ice bath. Next, a solution of 2.2 g (20 mmol) p-hydroxyphenol and 3.88 g (20 mmol) n-butyl p-hydroxybenzoate dissolved in 25 mL N,N-dimethylformamide was slowly added dropwise. The mixture was stirred continuously for 9 hours while maintaining the original temperature. After the reaction was complete, the reaction solution was filtered, concentrated, and dried, and intermediate 6 was obtained by column chromatography with a mass of 7.74 g (yield: 83%).

[0113]

[0114] 7.74 g (16.6 mmol) of intermediate 6 and 3.18 g (10.0 mmol) of zinc iodide were mixed thoroughly with 20 mL of N,N-dimethylformamide (DMF), and then heated at 150 °C for 11 hours. After the reaction was complete, the reaction system was allowed to cool naturally to room temperature and carefully transferred to 20 mL of ethanol to induce precipitation of the solid product. The solid was collected by filtration and washed repeatedly with ethanol to remove impurities, followed by drying under reduced pressure at 40 °C to remove residual solvent. Finally, 6.07 g of the target dye F (yield: 76%, purity: 98.0%) was successfully obtained by column chromatography purification. The following compounds were confirmed to be present in dye F based on H-NMR and MALDI-MS results.

[0115]

[0116] 1H NMR (DMSO-d6, ppm) δ:9.28(s, 4H), 7.93(d, 8H), 7.03(d, 8H), 6.75(d, 8H), 6.69 (d, 8H), 4.25(m, 8H), 1.75(m, 8H), 1.33(m, 8H), 0.96(m, 12H). [M / z]=1921.41, measured M=1921.44 <Synthesis Example 7: Synthesis of Dye G> 4.00 g (20 mmol) of tetrafluorophthalonitrile, 5.8 g (10.0 mmol) of potassium fluoride, and 25 Ml of N,N-dimethylformamide were mixed, and the mixture was then cooled in an ice bath. Next, a solution of 2.18 g (20 mmol) of p-hydroxyaniline and 3.32 g (20 mmol) of ethyl p-hydroxybenzoate dissolved in 25 Ml of N,N-dimethylformamide was slowly added dropwise. The mixture was stirred continuously for 12 hours while maintaining the original temperature. After the reaction was complete, the reaction solution was filtered, concentrated, and dried, and intermediate 7 was obtained by column chromatography with a mass of 7.08 g (yield: 81%).

[0117]

[0118] 7.08 g (16.2 mmol) of intermediate 7, 3.10 g (9.7 mmol) of zinc iodide, and 20 mL of N,N-dimethylformamide (DMF) were mixed thoroughly and then heated at 150 °C for 11 hours. After the reaction was complete, the reaction system was allowed to cool naturally to room temperature and carefully transferred to 20 mL of ethanol to induce precipitation of the solid product. The solid was collected by filtration and washed repeatedly with ethanol to remove impurities, followed by drying under reduced pressure at 40 °C to remove residual solvent. Finally, 6.07 g of the target dye G (yield: 83%, purity: 97.0%) was successfully obtained by column chromatography purification. The following compounds were confirmed to be present in dye G based on H-NMR and MALDI-MS results.

[0119]

[0120] 1H NMR (DMSO-d6, ppm) δ:8.36(s, 8H), 7.93(d, 8H), 7.03(d, 8H), 6.67(d, 8H), 6.42 (d, 8H), 4.29(m, 8H), 1.44(t, 12H). [M / z]=1805.34, measured M=1805.33 <Synthesis Example 8: Synthesis of Dye H> 4.00 g (20 mmol) tetrafluorophthalonitrile, 5.8 g (10.0 mmol) potassium fluoride, and 25 mL N,N-dimethylformamide were mixed and then cooled in an ice bath. Next, a solution of 2.18 g (20 mmol) p-hydroxyaniline and 3.88 g (20 mmol) n-butyl p-hydroxybenzoate dissolved in 25 mL N,N-dimethylformamide was slowly added dropwise. The mixture was stirred continuously for 13 hours while maintaining the original temperature. After the reaction was complete, the reaction solution was filtered, concentrated, and dried, and intermediate 8 was obtained by column chromatography with a mass of 7.16 g (yield: 77%).

[0121]

[0122] 7.16 g (15.4 mmol) of intermediate 8, 2.95 g (9.2 mmol) of zinc iodide, and 20 mL of N,N-dimethylformamide (DMF) were mixed thoroughly and then heated at 150 °C for 11 hours. After the reaction was complete, the reaction system was allowed to cool naturally to room temperature and carefully transferred to 20 mL of ethanol to induce precipitation of the solid product. The solid was collected by filtration and washed repeatedly with ethanol to remove impurities, followed by drying under reduced pressure at 40 °C to remove residual solvent. Finally, 5.39 g of the target dye H (yield: 73%, purity: 98.0%) was successfully obtained by column chromatography purification. Based on the results of ¹H NMR and MALDI-MS, the following compounds were confirmed to be present in dye H.

[0123]

[0124] 1H NMR (DMSO-d6, ppm) δ:8.36(s, 8H), 7.93(d, 8H), 7.03(d, 8H), 6.67(d, 8H), 6.42 (d, 8H), 4.25(m, 8H), 1.75(m, 8H), 1.33(m, 8H), 0.96(m, 12H). [M / z]=1917.46, measured M=1917.13.

[0125] This application also provides a method for preparing a dye resin composite, comprising the following steps; Phthalocyanine dye was slowly added to a solution containing resin under ice bath conditions, and the mixture was refluxed. After the reaction was completed, the solvent was concentrated to obtain a green flocculent dye-resin complex.

[0126] In some embodiments, the linking group includes at least one of ester group and amide group, the resin is an acrylic resin and contains acyl chloride group, the phthalocyanine dye contains hydroxyl and / or amine group, and while the phthalocyanine dye is slowly added to the solution containing the resin under ice bath, triethylamine is also added as a catalyst, which can cause the acyl chloride group to react with the hydroxyl and / or amine group to generate the linking group.

[0127] In some embodiments, the linking group includes at least one of ester group and amide group, the resin is an acrylic resin, and the phthalocyanine dye contains hydroxyl and / or amino groups. While the phthalocyanine dye is slowly added to the solution containing the resin under ice bath conditions, triethylamine is added as a catalyst, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI) and 1-hydroxybenzotriazole (HOBT) are added as condensing agents, which allows the carboxyl group to react with the hydroxyl and / or amino groups to generate the linking group.

[0128] This application provides dye resin composites from Examples 1 to 8, wherein: Example 1: Synthesis of Dye Resin Complex A 3.07 g (2.5 mmol) of dye molecule A was dissolved in 5 mL of dichloromethane and slowly heated in an ice bath. The resin was slowly added to a dichloromethane solution containing 19.0 g (approximately 2.0 mmol) of acrylic resin A. 1.0 mL of triethylamine was added as a catalyst, followed by the addition of 0.48 g (2.5 mmol) of EDCI and 0.34 g (2.5 mmol) of HOBT. The reaction was carried out in an ice bath for 1 hour, then refluxed at room temperature for 14 hours. After the reaction was completed, the solvent was concentrated to obtain a green flocculent dye-resin. The product was separated by column chromatography. The positions of the product and the reactants were compared on a thin-layer chromatography plate. If the positions were different, it proved that the grafting was successful. The molecular weight and acid value were then tested.

[0129] Example 2 Synthesis of dye-resin complex B 3.06 g (2.5 mmol) of dye molecule B was dissolved in 5 mL of dichloromethane and slowly added to a dichloromethane solution containing 19.0 g (approximately 2.0 mmol) of acrylic resin A under ice bath conditions. 1.0 mL of triethylamine was added as a catalyst, followed by the addition of 0.48 g (2.5 mmol) of EDCI and 0.34 g (2.5 mmol) of HOBT. The reaction was carried out under ice bath conditions for 1 h, and then refluxed at room temperature for 14 h. After the reaction was completed, the solvent was concentrated to obtain a green flocculent dye-resin. The product was separated by column chromatography. The positions of the product and the reactants were compared on a thin-layer chromatography plate. The difference in position indicated successful grafting. The molecular weight and acid value were then tested.

[0130] Example 3 Synthesis of dye-resin complex C 3.97 g (2.5 mmol) of dye molecule C was dissolved in 5 mL of dichloromethane and slowly added to a dichloromethane solution containing 19.0 g (approximately 2.0 mmol) of acrylic resin A under ice bath conditions. 1.0 mL of triethylamine was added as a catalyst, followed by the addition of 0.48 g (2.5 mmol) of EDCI and 0.34 g (2.5 mmol) of HOBT. The reaction was carried out under ice bath conditions for 1 h, and then refluxed at room temperature for 14 h. After the reaction was completed, the solvent was concentrated to obtain a green flocculent dye-resin. The product was separated by column chromatography, and the positions of the product and the reactants were compared on a thin-layer chromatography plate. The difference in position indicated successful grafting. The molecular weight and acid value were then tested.

[0131] Example 4 Synthesis of dye-resin complex D 3.94 g (2.5 mmol) of dye molecule D was dissolved in 5 mL of dichloromethane and slowly added to a dichloromethane solution containing 19.0 g (approximately 2.0 mmol) of acrylic resin A under ice bath conditions. 1.0 mL of triethylamine was added as a catalyst, followed by the addition of 0.48 g (2.5 mmol) of EDCI and 0.34 g (2.5 mmol) of HOBT. The reaction was carried out under ice bath conditions for 1 h, and then refluxed at room temperature for 14 h. After the reaction was completed, the solvent was concentrated to obtain a green flocculent dye-resin. The product was separated by column chromatography, and the positions of the product and the reactants were compared on a thin-layer chromatography plate. The difference in position indicated successful grafting. The molecular weight and acid value were then tested.

[0132] Example 5: Synthesis of Dye Resin Complex E 4.53 g (2.5 mmol) of dye molecule E was dissolved in 5 mL of dichloromethane and slowly added to a dichloromethane solution containing 19.0 g (approximately 2.0 mmol) of acrylic resin A under ice bath conditions. 1.0 mL of triethylamine was added as a catalyst, followed by the addition of 0.48 g (2.5 mmol) of EDCI and 0.34 g (2.5 mmol) of HOBT. The reaction was carried out under ice bath conditions for 1 h, and then refluxed at room temperature for 14 h. After the reaction was completed, the solvent was concentrated to obtain a green flocculent dye-resin. The product was separated by column chromatography, and the positions of the product and the reactants were compared on a thin-layer chromatography plate. The difference in position indicated successful grafting. The molecular weight and acid value were then tested.

[0133] Example 6 Synthesis of dye-resin complex F 4.81 g (2.5 mmol) of dye molecule F was dissolved in 5 mL of dichloromethane and slowly added to a dichloromethane solution containing 19.0 g (approximately 2.0 mmol) of acrylic resin A under ice bath conditions. 1.0 mL of triethylamine was added as a catalyst, followed by the addition of 0.48 g (2.5 mmol) of EDCI and 0.34 g (2.5 mmol) of HOBT. The reaction was carried out under ice bath conditions for 1 h, and then refluxed at room temperature for 14 h. After the reaction was completed, the solvent was concentrated to obtain a green flocculent dye-resin. The product was separated by column chromatography, and the positions of the product and the reactants were compared on a thin-layer chromatography plate. The difference in position indicated successful grafting. The molecular weight and acid value were then tested.

[0134] Example 7 Synthesis of dye-resin complex G 4.52 g (2.5 mmol) of dye molecule G was dissolved in 5 mL of dichloromethane and slowly added to a dichloromethane solution containing 19.0 g (approximately 2.0 mmol) of acrylic resin A under ice bath conditions. 1.0 mL of triethylamine was added as a catalyst, followed by the addition of 0.48 g (2.5 mmol) of EDCI and 0.34 g (2.5 mmol) of HOBT. The reaction was carried out under ice bath conditions for 1 h, and then refluxed at room temperature for 14 h. After the reaction was completed, the solvent was concentrated to obtain a green flocculent dye-resin. The product was separated by column chromatography, and the positions of the product and the reactants were compared on a thin-layer chromatography plate. The difference in position indicated successful grafting. The molecular weight and acid value were then tested.

[0135] Example 8 Synthesis of dye-resin complex H 4.80 g (2.5 mmol) of dye molecule H was dissolved in 5 mL of dichloromethane and slowly added to a dichloromethane solution containing 19.0 g (approximately 2.0 mmol) of acrylic resin A under ice bath conditions. 1.0 mL of triethylamine was added as a catalyst, followed by the addition of 0.48 g (2.5 mmol) of EDCI and 0.34 g (2.5 mmol) of HOBT. The reaction was carried out under ice bath conditions for 1 h, and then refluxed at room temperature for 14 h. After the reaction was completed, the solvent was concentrated to obtain a green flocculent dye-resin. The product was separated by column chromatography. The positions of the product and the reactants were compared on a thin-layer chromatography plate. The difference in position indicated successful grafting. The molecular weight and acid value were then tested.

[0136] In this embodiment, the acrylic resin is SP-DW-H1001-3 (Showa Denko Corporation, Japan), with a weight-average molecular weight of 9400 and an acid value of 82 (KOH mg / g).

[0137] The weight-average molecular weight and acid value of the dye resin composites in Examples 1 to 8 are shown in Table 1: Table 1

[0138] As can be seen from Table 1, the dye resin composite has a larger molecular weight and a different acid value compared to the acrylic resin. In addition, the dye resin composites of Examples 1 to 8 and the reaction raw materials showed differences in position after being compared on a thin-layer color plate, proving that the grafting was successful.

[0139] This application also provides a resin composition comprising the following components by weight percentage: Dye resin: 10%~16%; Monomer: 5-8%; Photoinitiator: 0.2-0.6%; The dye resin includes at least one of the above-mentioned dye resin composites, or the dye resin is prepared from the above-mentioned dye resin composite composition.

[0140] In this application, the monomer is the core active component for constructing the polymer resin network. It is typically a small organic molecule with unsaturated double bonds (such as acrylates, epoxides, etc.). Its molecular structure must simultaneously contain polymerizable functional groups and functionalized side groups. The former forms a cross-linked network during exposure-initiated free radical polymerization, while the latter enhances the interaction with the dye and substrate through hydrogen bonds, van der Waals forces, or chemical bonding. This application uses multifunctional monomers containing three or more functional groups participating in the cross-linking reaction. Preferred representative molecules include DPHA, DPHA-12, M402, M404, and M406, which have more active functional groups, faster reaction rates, larger molecular weights, and higher viscosity. M404 and DPHA are more preferred.

[0141] In this application, the photoinitiator acts as a "start switch" for the photochemical reaction. It is typically an organic compound containing specific light-absorbing groups (such as acetophenone, oxime esters, etc.). Its molecular structure allows it to efficiently absorb photon energy under specific wavelengths (such as deep ultraviolet or extreme ultraviolet). Through intramolecular charge transfer or bond breaking mechanisms, it generates free radicals or cationic active species. These active intermediates rapidly initiate the polymerization reaction of the resin monomers and crosslinking agents, causing the photoresist molecules in the exposed area to crosslink and solidify. The absorption spectrum of the photoinitiator must be precisely matched to the wavelength of the light source. Its quantum yield, thermal stability, and mobility directly affect the sensitivity, resolution, and pattern fidelity of the photoresist, ensuring accurate pattern transfer in complex photolithography processes.

[0142] This application selects two commonly used high-efficiency photoinitiators, oxime ester derivatives (PBG345, denoted as photoinitiator 1) and PBG3057, denoted as photoinitiator 3, and α-aminoketone derivatives (IGM369, denoted as photoinitiator 2), for research. Their structures and corresponding structures are shown below:

[0143] In some embodiments, the resin composition further includes at least one of a solvent, an additive, and a pigment.

[0144] In this embodiment of the application, the pigment includes yellow pigments, such as Y136, Y137, Y138, Y139, Y142, Y147, Y148, Y150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, etc., with Y138 being preferred as the colorant.

[0145] In this application, the solvent is the key medium for adjusting the coating performance. High-boiling-point, low-volatility organic solvents (such as propylene glycol methyl ether acetate (PGMEA), 3-methoxybutyl acetate, cyclohexanone, etc.) are typically selected. Their molecular polarity must be highly matched with the resin, monomers, and dyes to ensure that the photoresist system forms a uniform, defect-free film during spin coating or inkjet printing. In some preferred embodiments, the solvent includes PGMEA and 3-methoxybutyl acetate (MBA) solvents.

[0146] In the embodiments of this application, additives are used to improve the performance of photoresist, such as thermal inhibitors, defoamers, and leveling agents.

[0147] In some implementations, the mass percentages of solvent, additives, and pigments in the resin composition are as follows: Pigment: 2%~4%; Additives: 0.1%~0.2%; Solvent: Balance.

[0148] It is understood that the sum of the mass percentages of the components in the resin composition of this application is 100%.

[0149] This application also provides a method for preparing photoresist, including the following steps: The dye resin complex was dissolved in PGMEA solvent, and then the remaining solid components of the aforementioned resin composition were added. After mixing, the mixture was placed on a stirrer and stirred for 1 hour. After stirring, the mixture was filtered (the filter element was 1 μm). The photoresist was obtained after filtration.

[0150] The photoresists used in Examples 1 to 8 of this application are provided, and their components are shown in Table 2: Table 2

[0151] It should be noted that in Table 2, Y is selected from Y138, monomers 1 and 2 are M404 and DPHA respectively, photoinitiators 1 and 2 are PBG345 and IGM369 respectively, and the additives include Adeka's GPA-5001 and DIC's EFS-801.

[0152] This application also provides a photoresist for Comparative Example 1, the composition of which is the same as that of Example 1, except that the dye resin complex in Application Example 1 is replaced with a mixture of G58 and acrylic resin, that is, G58 is mixed with the remaining components by physical means, and the mass percentage of G58 and acrylic resin in the total system is 14%.

[0153] This application also provides photoresist color sheets and a method for preparing photoresist color sheets. The photoresist color sheet includes a substrate and a color film layer, and the color film layer is prepared by photoresist prepared from a pre-resin composition.

[0154] In this embodiment, the substrate needs to meet the basic requirements of transparency and moderate strength; the specific material is not strictly limited. Common optional materials include: polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, as well as thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, and poly(meth)acrylic acid resin, and various types of glass. From the perspective of heat resistance, glass is a more ideal choice.

[0155] The preparation method of photoresist color film is as follows: 1) Perform extreme ultraviolet (EUV) cleaning on the substrate; during EUV cleaning, oxygen molecules in the air absorb short-wavelength ultraviolet light and produce ozone and atomic oxygen; atomic oxygen has a high ability to effectively remove residual organic matter on the glass substrate. The effects of ultraviolet light of different wavelengths are different. In this embodiment, 172nm ultraviolet light is used for cleaning.

[0156] 2) Apply photoresist to the substrate; Coating methods are diverse, encompassing spin coating, planar blade coating, wire-wound bar coating, and spray coating. Among these coating technologies, spin coating demonstrates significant advantages for small-scale experiments. It not only uniformly coats colored photoresist but also effectively avoids hazy adhesion issues. Furthermore, it excels in suppressing impurity formation. Therefore, considering overall performance, spin coating is the preferred method for photoresist coating.

[0157] 3) Pre-bake the photoresist on the substrate at a temperature of 80℃~110℃ for 1-5 minutes. The pre-baking process in photoresist preparation involves precise control of temperature (80℃~110℃) and time (1-5 min) to allow the solvent to slowly evaporate until the residual amount is less than 10%. This enhances the adhesion between the photoresist and the substrate and avoids process problems caused by dark etching, bubble defects, and thermal effects during development. For thick photoresists, segmented baking is required, and for thermistor substrates, the temperature or time needs to be reduced. Optimizing parameters can significantly improve pattern resolution and process yield, and is a key step in ensuring the stability of the photolithography process.

[0158] 4) Precisely place the photomask on the coating and use the photomask to perform image exposure processing; This process requires strict control of exposure dose, focal plane position, and environmental vibration to ensure pattern resolution, overlay accuracy, and linewidth uniformity, laying a precise foundation for pattern transfer in subsequent development processes.

[0159] 5) By rinsing the exposed substrate with a specific developing solution (such as alkaline tetramethylammonium hydroxide TMAH solution or 5% potassium hydroxide developing solution) using a spray method, the photoresist in the unexposed area is precisely removed by taking advantage of the difference in the dissolution rate of the photoresist between the exposed and unexposed areas, thereby transforming the mask pattern into an actual visible relief structure. This process requires precise control of development time, temperature, and developer concentration to avoid pattern distortion caused by overdevelopment or residual defects caused by underdevelopment. At the same time, it is necessary to monitor the development rate and uniformity in real time to ensure the dimensional accuracy and color purity of the color filter array.

[0160] 6) Bake again at 180℃-250℃ to further catalyze the thermal cross-linking reaction of photoacid molecules in the exposed photoresist, thereby improving the etching resistance and thermal stability of the pattern; and by monitoring the film thickness change and contact angle parameters, ensure that the dimensional accuracy and surface flatness of the color filter array meet the mass production requirements of the display panel 100.

[0161] According to the above scheme, the prepared photoresist is sequentially coated onto a 10 cm × 10 cm glass slide, and the slide is coated, pre-baked, exposed, developed, and then baked to obtain a color sample.

[0162] This application provides photoresist color sheets C1 to C8, and a comparative photoresist color sheet C9. The photoresist color sheets C1 to C8 are prepared using the photoresist of Application Examples 1 to 8, respectively, and the comparative photoresist color sheet C9 is prepared using the comparative photoresist. The performance of the photoresist color sheets is shown in Table 5.

[0163] Table 5

[0164] It should be noted that the thermal stability in Table 5 refers to the chromaticity shift data before and after the hot baking (before and after step 6). The test method uses an MCPD instrument, specifically a micro-spectrophotometer (Lambda Vision, Japan). The instrument measures the parameters ΔL, Δa, and Δb to obtain ΔE, which is calculated using the formula ΔE=(Δa^2+Δb^2+ΔL^2)^0.5. Gx and Gy are chromaticity coordinates. A "○" indicates that no foreign object was observed, while an "X" indicates that a foreign object was observed.

[0165] As can be seen from Table 5, the thermal stability of the photoresist color sheets in Examples 1 to 8 is less than 2.5, which is better than that of the photoresist color sheets prepared by Comparative Example 1. Moreover, compared with the photoresist color sheets prepared by Comparative Example 1, they can be used to increase the brightness value and have no foreign matter, which proves that the dispersibility is good.

[0166] This application provides a resin composition containing the dye resin complex of the aforementioned embodiments. The dye resin complex connects phthalocyanine dye to the resin body via chemical bonds. After the film is prepared, the dye is uniformly dispersed in the film, which is beneficial to improving the display effect when the film is applied to a display device. Since the phthalocyanine dye is connected to the resin body via chemical bonds, the bonding force is enhanced, resulting in excellent thermal stability. When applied to the preparation of color filter layers, the color shift before and after high-temperature baking is small, thus improving the quality of the color filter.

[0167] At the same time, by adopting the chemical bonding method between dye and resin, the bonding ability is improved, and the hidden dangers of development residue and pattern defects are eliminated; in the subsequent photoresist preparation process, not only is the dispersion process reduced, but it is also environmentally friendly.

[0168] This application also provides a display panel 100, which includes a color filter layer 60, the color filter layer 60 being prepared from a dye resin composite as described in the foregoing embodiments, or from a resin composition as described in the foregoing embodiments.

[0169] In some embodiments, the display panel 100 is a liquid crystal display panel 100; See Figures 1-2The array substrate 10 and the opposing substrate 20 are disposed opposite to each other, and the liquid crystal layer 30 is disposed between the array substrate 10 and the opposing substrate 20. Further, the liquid crystal display panel 100 also includes a lower polarizer 40 disposed on the side of the array substrate 10 away from the liquid crystal layer 30 and an upper polarizer 50 disposed on the side of the opposing substrate 20 away from the array substrate 10.

[0170] The color filter layer 60 can be disposed on the opposing substrate 20 and located on the side of the opposing substrate 20 close to the liquid crystal layer 30, or the color filter layer 60 can be disposed on the array substrate 10 and located on the side of the array substrate 10 close to the liquid crystal layer 30.

[0171] It is understood that the liquid crystal display panel 100 in the embodiments of this application may also include other components, which are not limited to one by one.

[0172] See Figure 3 In some embodiments, the display panel 100 is an organic light-emitting display panel 100, which includes an organic light-emitting device 70.

[0173] Specifically, the organic light-emitting display panel 100 also includes an array substrate 10 and an encapsulation layer 80; the organic light-emitting device 70 is disposed on the array substrate 10 and electrically connected to the array substrate 10; the encapsulation layer 80 covers the array substrate 10 and the organic light-emitting device 70.

[0174] Understandably, the array substrate 10 is used to drive the organic light-emitting device 70 to emit light, and the encapsulation layer 80 is used to protect the organic light-emitting device 70.

[0175] Specifically, the organic light-emitting display panel 100 also includes a color filter layer 60 and a cover plate 90 located on the side of the encapsulation layer 80 away from the organic light-emitting device 70, with the color filter layer 60 located between the encapsulation layer 80 and the cover plate 90.

[0176] The above provides a detailed description of a dye resin composite, dye resin composite composition, resin composition, and display panel provided in the embodiments of this application. Specific examples have been used to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are only for the purpose of helping to understand the methods and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A dye-resin composite, characterized in that, The dye-resin complex comprises: Resin body; and, Dye groups attached to the resin matrix; The dye groups include phthalocyanine molecular groups.

2. The dye-resin composite according to claim 1, characterized in that, The resin matrix includes at least one resin backbone, the resin backbone includes a plurality of interconnected monomer units, and at least a portion of the monomer units are connected to the phthalocyanine molecular groups.

3. The dye-resin composite according to claim 2, characterized in that, The resin matrix includes at least two resin backbones, and at least a portion of the resin backbones are connected to the same phthalocyanine molecular group.

4. The dye-resin composite according to claim 1, characterized in that, The plurality of monomer units include at least one of acrylate monomer units and acrylic monomer units.

5. The dye-resin composite according to claim 1, characterized in that, The dye resin complex further includes a linking group that connects the resin matrix and the phthalocyanine molecular group.

6. The dye-resin composite according to claim 5, characterized in that, The linking group is selected from one or more combinations of ester group, amide group, enoyl group, imino group, siloxane group, sulfonate ester, and sulfonamide.

7. The dye-resin composite according to claim 1, characterized in that, The structure of the phthalocyanine molecular group is shown in formula (1): Where a is a positive integer greater than or equal to 1 and less than or equal to 16, n is a positive integer greater than or equal to 0 and less than or equal to 15, and a+n is less than or equal to 16, e is a positive integer greater than or equal to 1 and less than or equal to 5, f is a positive integer greater than or equal to 1 and less than or equal to 5, g is a positive integer greater than or equal to 0 and less than or equal to 4, and f+g is a positive integer greater than or equal to 1 and less than or equal to 5; In equation (1), R1 may be the same or different each time it appears, and R1 is selected from hydrogen atoms or halogen atoms; X may be the same or different each time it appears, and X is selected from one or more combinations of ether group, ester group, thioether group, sulfonic acid group, amino group, amide group, and siloxane group; Y may be the same or different each time it appears, and Y is selected from one or more combinations of alkyl, alkenyl, alkynyl, aryl, heteroaryl, halogen group, hydroxyl, carbonyl, aldehyde, ketone, carboxyl, ester, amino, amide, nitro, sulfonic acid, mercapto, cyano, alkoxy, acyl, phosphate, and silanol groups; M is selected from divalent metals; * indicates the connection site with the resin body.

8. The dye-resin composite according to claim 7, characterized in that, a+n is greater than or equal to 4 and less than or equal to 8; and / or, At least a portion of R1 in equation (1) is selected from F atoms, and the number of F atoms in equation (1) is greater than or equal to 4 and less than or equal to 12; and / or, At least a portion of the terminal groups of Y are alkyl groups having 2 to 4 carbon atoms.

9. The dye-resin composite according to any one of claims 1 to 8, characterized in that, The weight-average molecular weight of the dye resin composite is 10030~11600.

10. The dye-resin composite according to any one of claims 1 to 8, characterized in that, The acid value of the dye resin composite is 104~130.

11. A dye-resin composite composition, characterized in that, The dye-resin composite composition includes a resin and a phthalocyanine dye, wherein the resin has a first group, the phthalocyanine dye has a second group, and the first group and the second group generate a third group under applied conditions.

12. The dye-resin composite composition according to claim 11, characterized in that, The resin includes acrylic resins, and the molar ratio of the resin to the phthalocyanine dye is 1:(1~1.3).

13. The dye-resin composite composition according to claim 11, characterized in that, The first group includes one or more combinations of hydroxyl, carboxyl, aldehyde, ketone, amino, silanol, sulfonic acid, and acyl chloride groups; and / or, The second group is selected from one or more combinations of alkyl, alkenyl, alkynyl, aryl, aromatic, halogen, hydroxyl, carbonyl, aldehyde, ketone, carboxyl, ester, amino, amide, nitro, sulfonic acid, mercapto, cyano, alkoxy, acyl, phosphate, and silanol groups; and / or, The third group is selected from one or more combinations of ester group, amide group, enoyl group, imino group, siloxane group, sulfonate ester, and sulfonamide.

14. The dye-resin composite composition according to claim 11, characterized in that, The resin has a weight-average molecular weight of 9200-9600 and an acid value of 80-100.

15. The dye-resin composite composition according to claim 11, characterized in that, The molecular structure of the phthalocyanine dye is shown in formula (2): K may be the same or different each time it appears, and K is selected from one or more combinations of ether group, ester group, thioether group, sulfonic acid group, amino group, amide group, and siloxane group; A may appear the same or different each time it appears. A is selected from one or more combinations of alkyl, alkenyl, alkynyl, aryl, heteroaryl, halogen group, hydroxyl, carbonyl, aldehyde, ketone, carboxyl, ester, amino, amide, nitro, sulfonic acid, mercapto, cyano, alkoxy, acyl, phosphate, and silanol groups. E is selected from divalent metals; b is selected from positive integers greater than or equal to 1 and less than or equal to 16; h is selected from positive integers greater than or equal to 1 and less than or equal to 5; In equation (2), R2 may be the same or different each time it appears, and R2 is selected from hydrogen atoms or halogen atoms.

16. The dye-resin composite composition according to claim 15, characterized in that, b is greater than or equal to 4 and less than or equal to 8; and / or, At least a portion of R2 in equation (2) is selected from F atoms, and the number of F atoms in equation (2) is greater than or equal to 4 and less than or equal to 12; and / or, In formula (2), at least a portion of the terminal group of A is an alkyl group having 2 to 4 carbon atoms; and / or, At least part of A in formula (2) has the second group.

17. The dye-resin composite composition according to claim 11, characterized in that, The phthalocyanine dye is selected from at least one of the following compounds: 。 18. The dye-resin composite composition according to claim 12, characterized in that, The dye resin composite composition further includes at least one of a catalyst and a condensing agent, wherein the catalyst includes triethylamine, and the condensing agent includes at least one of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide salt, and 1-hydroxybenzotriazole.

19. A resin composition, characterized in that, The resin composition comprises the following components in weight percentage: Dye resin: 10%~16%; Monomer: 5-8%; Photoinitiator: 0.2-0.6%; The dye resin comprises at least one dye resin composite as described in any one of claims 1 to 10, or the dye resin is prepared from the dye resin composite composition as described in any one of claims 11 to 18.

20. A display panel, characterized in that, The display panel includes a color filter layer, which is prepared from a dye resin composite as described in any one of claims 1 to 10, or from a resin composition as described in claim 19.

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