Photosensitive colored resin composition, color filter and manufacturing method thereof, and liquid crystal display

Abstract

The invention relates to a photosensitive colored resin composition, a color filter, a manufacturing method of the color filter and a liquid crystal display. The photosensitive colored resin composition comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D) and a solvent (E). The nickel content in the photosensitive colored resin composition ranges from 1 ppm to 100 ppm, and the colorant (A) includes a triphenylmethane colorant (A-1). The manufacturing method of the color filter comprises the step of forming a pixel layer by using the photosensitive colored resin composition. The color filter is manufactured by the manufacturing method. The liquid crystal display comprises the color filter. By using the coloring agent (A) including the triphenylmethane coloring agent (A-1) and controlling the nickel content to be 1 ppm to 100 ppm, the size of foreign matters after a multi-stage thermal process in a pixel layer formed by the photosensitive colored resin composition can be reduced.

Description

Technical Field

[0001] This invention relates to a resin composition, a color filter, and a liquid crystal display, and particularly to a photosensitive coloring resin composition, a color filter, a method for manufacturing the same, and a liquid crystal display. Background Technology

[0002] Currently, color filters are widely used in color LCD displays, color fax machines, color cameras, and other applications. As the market demand for color LCD displays continues to expand, the manufacturing technology for color filters is becoming increasingly diversified, including methods such as dyeing, printing, electroplating, and dispersion. Among these, dispersion is the mainstream manufacturing method for color filters.

[0003] The dispersion method involves first dispersing a colorant in a photosensitive resin to form a photosensitive coloring resin composition. This composition is then coated onto a glass substrate and subjected to exposure and development steps to form pixel layers with a specific pattern. Repeating this coating, exposure, and development process three times yields the red (R), green (G), and blue (B) pixel layers of the color filter. Generally, to further improve the contrast of the color filter, a black matrix (or light-blocking layer) is placed between these pixel layers.

[0004] With the increasing demand for high-resolution displays (such as 4K / 8K LCD displays, Mini LED backlit displays, and microdisplays used in AR / VR), color filter manufacturing processes are evolving towards higher precision and more complex process conditions. Consequently, in pixel layers formed from existing photosensitive coloring resin compositions, changes in the process conditions for forming the pixel layer can easily lead to the formation of micron-sized particles due to crystallization or localized aggregation. This increases the size of foreign matter, resulting in serious defects in high pixel density (Pixel Per Inch, PPI) displays.

[0005] Therefore, how to reduce the size of foreign matter generated by the manufacturing process in the pixel layer formed by the photosensitive coloring resin composition in the color filter, so as to avoid serious defects in displays with high pixel density, is a problem that technicians in this field urgently need to solve. Summary of the Invention

[0006] This invention was developed to gain a deeper understanding of foreign matter formation in pixel layers. The results showed that, in order to meet the more complex manufacturing requirements of high-resolution displays, when fabricating color filters using pixel layers formed from photosensitive coloring resin compositions, the pixel layers need to undergo multiple thermal processes. However, this process causes the photosensitive coloring resin compositions to form foreign matter (hereinafter referred to as "post-thermal process foreign matter") due to crystallization or local aggregation. Therefore, the primary objective of this invention is to provide a photosensitive coloring resin composition that can reduce the size of post-thermal process foreign matter in pixel layers.

[0007] The photosensitive coloring resin composition of the present invention comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E).

[0008] The nickel content in the photosensitive coloring resin composition ranges from 1 ppm to 100 ppm, and the colorant (A) includes a triphenylmethane-based colorant (A-1).

[0009] In the photosensitive coloring resin composition of the present invention, the nickel content in the photosensitive coloring resin composition ranges from 2 ppm to 80 ppm.

[0010] In the photosensitive coloring resin composition of the present invention, the nickel content in the photosensitive coloring resin composition ranges from 3 ppm to 50 ppm.

[0011] In the photosensitive coloring resin composition of the present invention, the calcium content in the photosensitive coloring resin composition ranges from 1 ppm to 100 ppm.

[0012] In the photosensitive coloring resin composition of the present invention, the calcium content in the photosensitive coloring resin composition ranges from 5 ppm to 50 ppm.

[0013] In the photosensitive coloring resin composition of the present invention, the triphenylmethane-based colorant (A-1) comprises a triphenylmethane-based colorant having a structure as shown in formula (I-1-1).

[0014] (I-1-1)

[0015] In equation (I-1-1),

[0016] A represents an organic group with a p-valence, wherein the carbon atom in the organic group directly bonded to N does not have a π bond; the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group; the carbon chain of the aliphatic hydrocarbon group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom; the carbon chain of the aromatic group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom.

[0017] R 1 R 2 R 3 R 4 and R 5 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, R 2 With R 3 They can bond together to form a ring structure, R 4 With R 5 They can bond together to form a ring structure, multiple R 1 R 2 R 3 R 4 and R 5 Each can be the same or different.

[0018] Ar 1 Indicates substituted or unsubstituted divalent aromatic groups, multiple Ar 1 Each can be the same or different.

[0019] B q- Indicates anion.

[0020] p represents an integer greater than or equal to 1.

[0021] r and s each independently represent integers greater than 1.

[0022] In the photosensitive coloring resin composition of the present invention, B q- It is a heterogeneous multiple acid anion containing at least one of molybdenum and tungsten.

[0023] A second objective of this invention is to provide a method for manufacturing a color filter.

[0024] The method for manufacturing a color filter of the present invention includes forming a pixel layer using the photosensitive coloring resin composition described above.

[0025] A third objective of this invention is to provide a color filter.

[0026] The color filter of the present invention is manufactured by the color filter manufacturing method described above.

[0027] The fourth objective of this invention is to provide a liquid crystal display.

[0028] The liquid crystal display of the present invention includes the color filter as described above.

[0029] The beneficial effects of the present invention are as follows: by using the colorant (A) including the triphenylmethane-based colorant (A-1), and simultaneously controlling the nickel content in the photosensitive coloring resin composition to be within the range of 1ppm to 100ppm, the foreign matter size in the pixel layer formed by the photosensitive coloring resin composition is reduced after the multi-stage thermal process, thereby enabling the pixel layer to meet the requirements of high-resolution displays when used to prepare color filters and liquid crystal displays. Detailed Implementation

[0030] It should be noted that when fabricating color filters using pixel layers formed from photosensitive coloring resin compositions, foreign matter may form due to the influence of different process conditions. In particular, the pixel layers formed from photosensitive coloring resin compositions require multiple high-temperature processes (i.e., multi-stage thermal processes), such as multi-stage pre-bake, multi-stage post-bake, and subsequent transparent electrode sputtering or encapsulation annealing, to obtain the color filter. However, these multi-stage high-temperature processes result in an extremely high cumulative thermal budget (CTB) for the pixel layer. Furthermore, under such multi-stage high-temperature process conditions, the photosensitive coloring resin compositions in the pixel layer are prone to crystallization or local aggregation, forming micron-sized particles, which increases the size of foreign matter. Therefore, using pixel layers containing excessively large foreign matter generated by multi-stage high-temperature processes to fabricate color filters will cause serious defects in high-pixel-density liquid crystal displays. In view of this, the present invention aims to reduce the size of foreign matter (hereinafter referred to as "post-multi-stage thermal process foreign matter") generated in the pixel layer by controlling the nickel content in the photosensitive coloring resin composition to a range of 1 ppm to 100 ppm and using a colorant (A) including a triphenylmethane-based colorant (A-1).

[0031] Photosensitive coloring resin composition

[0032] This invention provides a photosensitive coloring resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E). The nickel content in the photosensitive coloring resin composition ranges from 1 ppm to 100 ppm, and the colorant (A) includes a triphenylmethane-based colorant (A-1). Furthermore, in some embodiments of this invention, the photosensitive coloring resin composition may selectively include an additive (F).

[0033] In some embodiments of the present invention, in order to further reduce the size of foreign matter after multi-stage thermal processing in the pixel layer formed by the photosensitive coloring resin composition in the color filter, preferably, the nickel content in the photosensitive coloring resin composition ranges from 2 ppm to 80 ppm; more preferably, the nickel content in the photosensitive coloring resin composition ranges from 3 ppm to 50 ppm.

[0034] In this invention, if the nickel content in the photosensitive coloring resin composition does not fall within the range of 1ppm to 100ppm, the pixel layer formed by the photosensitive coloring resin composition in the color filter is prone to the problem of excessively large foreign matter size after multi-stage thermal processing.

[0035] It should be noted that although the detailed mechanism by which the nickel content in the aforementioned photosensitive coloring resin composition does not fall within the range of 1ppm to 100ppm, resulting in excessively large foreign matter size in the pixel layer formed by the photosensitive coloring resin composition after multi-stage thermal processing is still unclear, it is speculated that the following factors may be involved: due to nickel's appropriately high charge density and good thermal stability, nickel can form stable but reversible coordination bonds with the nitrogen atoms of the triphenylmethane-based colorant (A-1) or the carboxyl and hydroxyl groups in the alkali-soluble resin (B), thereby disrupting the π-π stacking between molecules and inhibiting the rearrangement and crystallization of the triphenylmethane-based colorant (A-1) under multi-stage thermal processing, thereby reducing the size of foreign matter after multi-stage thermal processing. Therefore, when the nickel content is less than 1 ppm and too low, the stabilizing effect of inhibiting the rearrangement and crystallization of the triphenylmethane colorant (A-1) is insufficient. When the nickel content is too high, nickel salt precipitation may occur, which may result in the foreign matter being too large after the multi-stage thermal process.

[0036] In some embodiments of the present invention, in order to further reduce the size of foreign matter after multi-stage thermal processing in the pixel layer formed by the photosensitive coloring resin composition in the color filter, the calcium content in the photosensitive coloring resin composition ranges from 1 ppm to 100 ppm; preferably, the calcium content in the photosensitive coloring resin composition ranges from 3 ppm to 80 ppm; more preferably, the calcium content in the photosensitive coloring resin composition ranges from 5 ppm to 50 ppm.

[0037] It should be noted that although the detailed mechanism by which the calcium content in the aforementioned photosensitive coloring resin composition is 1 ppm to 100 ppm, further reducing the size of foreign matter in the pixel layer formed by the photosensitive coloring resin composition after multi-stage thermal processing, is not yet clear, it is speculated that the following factors may be involved: Since calcium has a large ionic radius and a low charge density, through ionic spacing and electrostatic shielding, it further reduces the attraction between the triphenylmethane-based colorants (A-1). Therefore, through the bimetallic synergistic effect of nickel and calcium, a stabilizing effect can be achieved even when the concentrations of nickel and calcium are relatively low, further reducing the size of foreign matter after multi-stage thermal processing.

[0038] <Colorant (A)>

[0039] The colorant (A) includes a triphenylmethane-based colorant (A-1). In some embodiments of the present invention, the colorant (A) may further include other colorants (A-2) besides the triphenylmethane-based colorant (A-1).

[0040] [Triphenylmethane-based colorant (A-1)]

[0041] The triphenylmethane-based colorant (A-1) has a structure as shown in formula (I-1).

[0042] (I-1)

[0043] In the aforementioned formula (I-1),

[0044] A represents an organic group with a p-valence, wherein the carbon atom in the organic group directly bonded to N does not have a π bond; the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group; the carbon chain of the aliphatic hydrocarbon group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom; the carbon chain of the aromatic group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom.

[0045] R 1 R 2 R 3 R 4 and R 5 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, R 2 With R 3 They can bond together to form a ring structure, R 4 With R 5 They can bond together to form a ring structure, multiple R 1 R 2 R 3 R4 and R 5 Each can be the same or different.

[0046] Ar 1 Indicates substituted or unsubstituted divalent aromatic groups, multiple Ar 1 Each can be the same or different.

[0047] p represents an integer greater than or equal to 1.

[0048] In formula (I-1), the p-valent organic group represented by A has a carbon atom directly bonded to a nitrogen atom (N) that does not have a π bond. The organic group represents an aliphatic hydrocarbon group with at least a saturated aliphatic hydrocarbon group at the end directly bonded to N, or an aromatic group containing such an aliphatic hydrocarbon group. The carbon chain of the aliphatic hydrocarbon group may contain oxygen (O), sulfur (S), and nitrogen (N), and the carbon chain of the aromatic group may also contain O, S, and N. Because the carbon atom directly bonded to N by the organic group does not have a π bond, the color characteristics such as hue or transmittance of the cationic chromogenic site are not affected by the bonding group, i.e., A, or other chromogenic sites, and can maintain the same color as the monomer.

[0049] In formula (I-1), the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N can be any of straight-chain, branched, or cyclic, provided that the carbon atom at the end directly bonded to N does not have a π bond. The carbon atoms other than the terminal carbon atoms can have unsaturated bonds and can have substituents. The carbon chain of the substituent can contain O, S, or N. The carbon chain of the substituent can, for example, contain carbonyl, carboxyl, oxycarbonyl, or amide groups, and the hydrogen atom can be substituted with a halogen atom, etc.

[0050] Furthermore, in A of the formula (I-1), the aromatic group having the aliphatic hydrocarbon group can be listed as a monocyclic or polycyclic aromatic group having at least one aliphatic hydrocarbon group at the end directly bonded to N, which may have substituents or be a heterocycle containing O, S, and N.

[0051] In the A of the formula (I-1), from the viewpoint of the strength of the skeleton, it is preferable that the A contains a cyclic aliphatic hydrocarbon group or an aromatic group.

[0052] In the A of formula (I-1), from the viewpoint of the robustness of the skeleton, it is preferable that the cyclic aliphatic hydrocarbon group of A is a bridged alicyclic hydrocarbon group. A bridged alicyclic hydrocarbon group refers to a polycyclic aliphatic hydrocarbon group having a cross-linked structure within an aliphatic ring or having a polycyclic structure. Examples of bridged alicyclic hydrocarbon groups include norbornane, bicyclic [2.2.2]octane, and adamantane. Preferably, the bridged alicyclic hydrocarbon group is norbornane. Furthermore, the aromatic group can include groups containing a benzene ring or a naphthalene ring. Preferably, the aromatic group is a group containing a benzene ring. For example, when A is a divalent organic group, examples include straight-chain, branched, or cyclic alkylene groups with 1 to 20 carbon atoms, or aromatic groups such as xylylene substituted with two alkylene groups with 1 to 20 carbon atoms.

[0053] In formula (I-1), the valence p is the number of chromogenic cationic sites constituting the cation, and p represents an integer of 1 or more. In the colorant, from the viewpoint of heat resistance, it is preferable that the valence p of the cation is 2 or more, more preferably, the valence p of the cation is 3 or more. There is no particular upper limit to p, but from the viewpoint of ease of manufacture, it is preferable that p is 4 or less, more preferably, p is 3 or less.

[0054] In the above formula (I-1), R 1 The R 2 The R 3 The R 4 and the R 5 Each can be independently represented by a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

[0055] In the above formula (I-1), R 1 The R 2 The R 3 The R 4 and the R 5 The alkyl group is not particularly limited, and examples include straight-chain alkyl or branched alkyl groups having 1 to 20 carbon atoms. Preferably, the alkyl group is a straight-chain alkyl or branched alkyl group having 1 to 8 carbon atoms, and more preferably, the alkyl group is a straight-chain alkyl or branched alkyl group having 1 to 5 carbon atoms. From the viewpoint of pixel brightness, it is particularly preferred that the R... 1 The R 2 The R 3 The R 4 and the R 5 The alkyl group is ethyl or methyl. There are no particular restrictions on the substituents that the alkyl group may have, and examples include aryl, halogen atoms, hydroxyl, etc., and substituted alkyl groups may include aralkyl groups of benzyl, etc.

[0056] In the above formula (I-1), R 1 The R 2 The R 3 The R 4 and the R 5 There are no particular restrictions on the aryl group, and examples include phenyl, naphthyl, etc. There are no particular restrictions on the substituents that the aryl group may have, and examples include alkyl groups, halogen atoms, etc.

[0057] The so-called "R" 2 With R 3 They can bond together to form a ring structure, R 4 With R 5 "Can bond together to form a ring structure" refers to "R" 2 With R 3 They can form ring structures by bonding together through nitrogen atoms, R 4 With R 5 "They can form ring structures by bonding with each other through nitrogen atoms." There are no particular restrictions on the ring structure, and examples include pyrrolidine rings, piperidine rings, or morpholine rings.

[0058] In the above formula (I-1), from the viewpoint of chemical stability, preferably, the R 1 The R 2 The R 3 The R 4 and the R 5 Each of the above can independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or the aforementioned R. 2 With the R 3 The R are bonded together to form a ring structure. 4 With the R 5 They are bonded together to form a ring structure, wherein the ring structure may include pyrrolidine ring, piperidine ring, or morpholine ring.

[0059] In the above formula (I-1), R 1 The R 2 The R 3 The R 4 and the R 5 Each can independently form the above structure, that is, multiple R 1 R 2 R 3 R 4 and R 5 Each can be the same or different. From the viewpoint of color purity, preferably, the R... 1 It is a hydrogen atom. More preferably, from the viewpoint of ease of manufacture and raw material supply, the R... 2 The R 3 The R4 and the R 5 They are all the same.

[0060] In the above formula (I-1), the Ar 1 There are no particular restrictions on whether the divalent aromatic groups in the form are substituted or unsubstituted; multiple Ar groups are allowed. 1 Each can be the same or different. The Ar... 1 The aromatic groups in the middle can be the same as those listed in A.

[0061] In the above formula (I-1), preferably, the Ar 1 It is an aromatic group with 6 to 20 carbon atoms, substituted or unsubstituted, more preferably, the Ar 1 It is an aromatic group containing a condensed polycyclic carbocyclic ring, with 10 to 14 carbon atoms, whether substituted or unsubstituted. From the viewpoint of simple structure and low raw material cost, the Ar... 1 It is phenylene or naphthylene.

[0062] In the above formula (I-1), there are multiple R within one molecule. 1 R 2 R 3 R 4 R 5 and Ar 1 They can be the same or different. Through the aforementioned R... 1 The R 2 The R 3 The R 4 The R 5 and the Ar 1 The combination can be adjusted to the desired color.

[0063] The structure shown in formula (I-1) is a cation with a valence of more than one, which can combine with an anion with a valence of more than one. The anion is, for example, B. q- .

[0064] It is worth noting that when the compound represented by formula (I-1) is in a state containing anion and cation with a valence of more than two, the structure represented by formula (I-1) (i.e., the cation) and the B q- (i.e., anions) can form aggregates. Anions and cations are not simply ionicly bonded one molecule to one molecule, but rather form molecular assemblies by assembling multiple molecules through ionic bonds. Therefore, the apparent molecular weight of such aggregates is higher than that of existing lake pigments. Generally, it is speculated that the structure shown in formula (I-1) (i.e., the cation) and the B...q- The aggregates formed by (i.e., anions) have a stronger cohesive force in the solid state and reduce thermal motion, which can inhibit the dissociation of ion pairs or the decomposition of cations, making them more difficult to fade than existing lake pigments.

[0065] In some embodiments of the present invention, the structure shown in formula (I-1) is a cation with a valence of more than one monovalent combined with the B q- Given an anion, the molecular assembly can be represented, for example, by the structure shown in the following formula (I-1-1).

[0066] (I-1-1)

[0067] In the above formula (I-1-1), A and Ar 1 R 1 R 2 R 3 R 4 R 5 And p is the same as in equation (I-1), so it will not be repeated here. B q- Represents anion. r and s each independently represent integers greater than 1.

[0068] In formula (I-1-1), r represents the number of cations, and s represents the number of anions in the molecular assembly. Each of r and s independently represents an integer greater than or equal to 1. When r represents 2 or more, the multiple cations in the molecular assembly can be used individually or in combination with two or more types. Similarly, when s is 2 or more, the multiple anions in the molecular assembly can be used individually or in combination with two or more types.

[0069] Furthermore, in the aforementioned formula (I-1-1), the B q- (i.e., anion) is not particularly limited and can be organic or inorganic anion. Here, "organic anion" refers to anion containing at least one carbon atom. "Inorganic anion" refers to anion that does not contain a carbon atom. In this invention, from the viewpoint of pixel brightness, preferably, the B... q- It is an inorganic anion.

[0070] In some embodiments of the present invention, in the B q- In the case of organic anions, there are no particular restrictions on their structure, and examples can be found in International Publication No. 2012 / 144520.

[0071] From the viewpoint of colorant stability, preferably, said B q-An organic anion having two or more monovalent anionic substituents in one molecule. Specific examples of such anionic substituents include -SO₂N. - SO2CH3, -SO2N - COCH3, -SO2N - SO2CF3, -SO2N - COCF3, -CF2SO2N - SO2CH3, -CF2SO2N - COCH3、-CF2SO2N - SO2CF3, -CF2SO2N - Imide groups such as COCF3, -SO3 - (i.e., sulfonate anion), -CF2SO3 - -PO3 2- -COO - -CF2PO3 2- and -CF2COO - From the viewpoint that high acidity effectively stabilizes cations and maintains color, it is preferable that the anionic substituent is an imide group or -SO3. - -CF2SO3 - More preferably, the anionic substituent is -SO3. - (Sulfonate group). In the case of multiple substituted anionic substituents, the same substituents or different substituents may be used.

[0072] On the other hand, in the B q- In the case of inorganic anions, there are no particular restrictions on their structure; examples include anions of oxyacids with a valence of divalent or higher (e.g., phosphate ions, sulfate ions, chromate ions, tungstate ions (WO4)). 2- ), molybdate ions (MoO4) 2- [etc.], multiple acid anions formed by the condensation of multiple oxyacids, halogen anions, or mixtures thereof.

[0073] The multiple acid anions can be listed as heterogeneous multiple acid anions (M y O z ) q- or heteropolyacid anion (XM) y O z ) q-In the above ionic formulas, M represents polyatoms, X represents heteroatoms, y represents the composition ratio of polyatoms, and z represents the composition ratio of oxygen atoms. Examples of polyatoms M include molybdenum (Mo), tungsten (W), vanadium (V), titanium (Ti), or niobium (Nb). Examples of heteroatoms X include silicon (Si), phosphorus (P), arsenic (As), sulfur (S), iron (Fe), and cobalt (Co). Furthermore, heterospecific multiple acid anions and heteromultiacid anions may also contain Na. + or H + Such as cations.

[0074] In some embodiments of the present invention, preferably, the B q- It is a heterodimeric multiple acid anion containing at least one of molybdenum (Mo) and tungsten (W), more preferably, the B q- It is a heterogeneous multiple acid anion containing at least the q-valence of tungsten. When the B of the present invention... q- When the component contains at least one of molybdenum (Mo) and tungsten (W) heterogeneous multiple acid anions, the size of foreign matter in the pixel layer formed by the photosensitive coloring resin composition after multi-stage thermal processing in the color filter can be further reduced.

[0075] The multiple acid anion containing at least one of molybdenum (Mo) and tungsten (W) can be exemplified by tungstate ions [W], which belong to heterologous multiple acids. 10 O 32 ] 4- Molybdate ions [Mo6O] 19 ] 2- phosphotungstic acid ions [PW] belong to heteropolyacid ions. 12 O 40 ] 3- silicotungstic acid ions [SiW] 12 O 40 ] 4- phosphomolybdate ions [PMo] 12 O 40 ] 3- phosphotungstic molybdenum ion [PW] 12-a Mo a O 40 ] 3- H3[PW 2- b Mo b O7] 4- wait.

[0076] In the multiple acid anion containing at least one of molybdenum (Mo) and tungsten (W), the molar ratio of tungsten to molybdenum is not particularly limited. From the viewpoint of pixel brightness, it is preferable that the molar ratio of tungsten to molybdenum is between 100:0 and 90:10.

[0077] In some embodiments of the present invention, the B q- To represent the imide group, halide anion, or the multiple acid anion mentioned above.

[0078] In some embodiments of the present invention, preferably, the B q- For chloride ions, [PW 12 O 40 ] 3- [PW] 11.76 Mo 0.24 O 40 ] 3- , or combinations thereof.

[0079] Furthermore, there are no particular limitations on the method of preparing the structure shown in formula (I-1) and the compound shown in formula (I-1-1), for example, it can be prepared with reference to International Publication No. 2012 / 144520.

[0080] Specific examples of the compounds represented by formula (I-1-1) may include at least one of compounds (1) to (29). Each of compounds (1) to (20) and compounds (22) to (28) contains a cation and a heterologous multiple acid anion.

[0081]

[0082] Compound (1)

[0083]

[0084] Compound (2)

[0085]

[0086] Compound (3)

[0087]

[0088] Compound (4)

[0089]

[0090] Compound (5)

[0091]

[0092] Compound (6)

[0093]

[0094] Compound (7)

[0095]

[0096] Compound (8)

[0097]

[0098] Compound (9)

[0099]

[0100] Compound (10)

[0101]

[0102] Compound (11)

[0103]

[0104] Compound (12)

[0105]

[0106] Compound (13)

[0107]

[0108] Compound (14)

[0109]

[0110] Compound (15)

[0111]

[0112] Compound (16)

[0113]

[0114] Compound (17)

[0115]

[0116] Compound (18)

[0117]

[0118] Compound (19)

[0119]

[0120] Compound (20)

[0121]

[0122] Compound (21)

[0123]

[0124] Compound (22)

[0125]

[0126] Compound (23)

[0127]

[0128] Compound (24)

[0129]

[0130] Compound (25)

[0131]

[0132] Compound (26)

[0133]

[0134] Compound (27)

[0135]

[0136] Compound (28)

[0137]

[0138] Compound (29)

[0139] In some embodiments of the present invention, based on a total weight of 100 wt% of the solid components of the photosensitive coloring resin composition, the content of the triphenylmethane colorant (A-1) ranges from 0.5 wt% to 60 wt%; preferably, the content of the triphenylmethane colorant (A-1) ranges from 1 wt% to 55 wt%; more preferably, the content of the triphenylmethane colorant (A-1) ranges from 5 wt% to 50 wt%.

[0140] [Other colorants (A-2)]

[0141] The other colorant (A-2) may be an inorganic pigment, an organic pigment, a dye, or a combination thereof.

[0142] The inorganic pigment may be a metal compound such as a metal oxide or a metal complex salt. Examples of inorganic pigments include oxides of metals such as iron (Fe), cobalt (Co), cadmium (Cd), lead (Pb), copper (Cu), titanium (Ti), magnesium (Mg), chromium (Cr), zinc (Zn), and antimony (Sb), composite oxides of the aforementioned metals, metal complex salts, or combinations thereof.

[0143] Specific examples of the organic pigments mentioned include CI pigment yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 16 7, 168, 175; CI Pigment Orange l, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI Pigment Red l, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:l, 48:2, 48:3, 48:4, 49:l, 49:2, 50:1, 52:l, 53:l, 57, 57:l ,57:2,58:2,58:4,60:l,63:l,63:2,64:l,81:l,83,88,90:l,97,101,102,104,105,106,108,112,113,114,122,123,144,1 46, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 2 08, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; CI Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38, 39, 40, 50; CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 21, 22, 60, 61, 64, 66; CI Pigment Green 7, 36, 37, 42, 58; CI Pigment Brown 23, 25, 28; CI Pigment Black 1, 7; or combinations thereof.

[0144] The dyes include, but are not limited to, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, or combinations thereof.

[0145] The anthraquinone dyes include, but are not limited to, Badblue 4, Acid Blue 40, Acid Green 25, Reactive Blue 19, Reactive Blue 49, Disperse Red 60, Disperse Blue 56, Disperse Blue 60, or combinations thereof.

[0146] The phthalocyanine dyes include, but are not limited to, Basic Blue 5, Direct Blue 86, or combinations thereof.

[0147] The quinone imine dyes include, but are not limited to, Basic Blue 3, Basic Blue 9, or combinations thereof.

[0148] The quinoline dyes include, but are not limited to, CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, or combinations thereof.

[0149] The nitro dyes include, but are not limited to, Acid Yellow 1, Acid Orange 3, Disperse Yellow 42, or combinations thereof.

[0150] The other colorants (A-2) can be used alone or in combination.

[0151] The average particle size of the other colorant (A-2) may be from 10 nm to 200 nm; preferably, the average particle size of the other colorant (A-2) is from 20 nm to 150 nm; more preferably, the average particle size of the other colorant (A-2) is from 30 nm to 130 nm.

[0152] In some embodiments of the present invention, based on a total solid weight of 100 wt% of the photosensitive coloring resin composition, the content of the other colorant (A-2) may range from 0 wt% to 40 wt%; preferably, the content of the other colorant (A-2) ranges from 0 wt% to 35 wt%; more preferably, the content of the other colorant (A-2) ranges from 0 wt% to 30 wt%.

[0153] In the photosensitive coloring resin composition of the present invention, preferably, the colorant (A) is used by dispersing it in a solvent using a dispersant. In some embodiments of the present invention, the dispersant may be suitably selected from existing dispersants. Examples of dispersants include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polysiloxane surfactants, fluorinated surfactants, and combinations thereof. The dispersants listed above may be non-polymeric or polymeric dispersants. From the viewpoint of achieving uniform and fine dispersion, the dispersant is preferably a polymeric dispersant.

[0154] The polymeric dispersants may include (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial) amine salts, (partial) ammonium salts, or (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylates or modified products of the above compounds; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives [i.e., amides or bases thereof obtained by reacting poly(lower alkylimine) with polyesters containing free carboxyl groups]; polyallylamine derivatives [i.e., reaction products obtained by reacting polyallylamine with one or more compounds selected from polyesters, polyamides, or cocondensates of esters and amides (polyesteramides) containing free carboxyl groups], or combinations thereof.

[0155] In some embodiments of the present invention, from the viewpoint of better dispersibility of the colorant (A) and good dispersion stability, the polymeric dispersant is preferably a polymeric dispersant containing nitrogen atoms in the main chain or side chain and having an amine valence.

[0156] Specific examples of polymeric dispersants containing nitrogen atoms in the main chain or side chain are listed below.

[0157] Commercially available examples of (partial) amine salts, (partial) ammonium salts, or (partial) alkylamine salts of the (co)polymers of unsaturated carboxylic acids such as polyacrylic acid include Disperbyk 2000 and Disperbyk 2001 [all manufactured by BYK-Chemie].

[0158] Commercially available polyurethane products include Disperbyk 161 [manufactured by BYK-Chemie].

[0159] Commercially available unsaturated polyamides include Disperbyk 101 and Disperbyk 130 [manufactured by BYK-Chemie].

[0160] Commercially available examples of the aforementioned polyethylene imide derivatives include Solsperse 33500 [manufactured by Lubrizol Corporation, Japan], etc.

[0161] Commercially available examples of the polyallylamine derivatives include Ajisper PB821, Ajisper PB822, Ajisper PB824, and Ajisper PB827 [manufactured by Ajinomoto Fine-Techno].

[0162] Other commercially available dispersants include Dysperbyk 116, Dysperbyk 140, Dysperbyk 160, Dysperbyk 162, Dysperbyk 163, Dysperbyk 164, Dysperbyk 166, Dysperbyk 167, Dysperbyk 168, Dysperbyk 170, Dysperbyk 171, Dysperbyk 174, Dysperbyk 182, and Dysperbyk 2050 [all manufactured by BYK-Chemie]; EFKA4046 and EFKA4047 [all manufactured by EFKA Chemicals Co.]; and Solsperse 12000, Solsperse 13250, and Solsperse... 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse24000SC, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 33500, Solsperse 35200, Solsperse 37500 [all manufactured by Lubrizol, Japan]; Ajisper PB711, Ajisper 823, Ajisper 880 [all manufactured by Ajinomoto Fine-Techno], etc.

[0163] There are no particular restrictions on the amount of dispersant used; it can be adjusted appropriately according to needs.

[0164] In some embodiments of the present invention, based on a total weight of 100 wt% of the solid components of the photosensitive coloring resin composition, the content of the colorant (A) can range from 0.5 wt% to 60 wt%; preferably, the content of the colorant (A) ranges from 1 wt% to 55 wt%; more preferably, the content of the colorant (A) ranges from 5 wt% to 50 wt%.

[0165] <Alkali-soluble resin (B)>

[0166] The alkali-soluble resin (B) may include a first alkali-soluble resin (B-1). In some embodiments of the present invention, the alkali-soluble resin (B) may further include a second alkali-soluble resin (B-2).

[0167] [First base-soluble resin (B-1)]

[0168] The first alkali-soluble resin (B-1) is obtained by copolymerizing an ethylene unsaturated monomer (b-1-1) containing a carboxylic acid group with other copolymerizable ethylene unsaturated monomers (b-1-2).

[0169] The carboxylic acid-containing vinyl unsaturated monomer (b-1-1) can be used alone or in combination, and the carboxylic acid-containing vinyl unsaturated monomer (b-1-1) includes, but is not limited to, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid (MAA), butenoic acid, α-chloroacrylic acid, ethylacrylic acid, cinnamic acid, 2-acryloyloxysuccinate, or 2-methacryloyloxyethyl succinate monoester (HOMS); unsaturated dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride; and unsaturated polycarboxylic acids (anhydrides) with three or more carboxylic acid groups. In some embodiments of the present invention, preferably, the carboxylic acid-containing vinyl unsaturated monomer (b-1-1) is acrylic acid, methacrylic acid, 2-acryloylethoxysuccinate, 2-methacryloylethoxysuccinate, or a combination thereof; more preferably, the carboxylic acid-containing vinyl unsaturated monomer (b-1-1) is 2-acryloylethoxysuccinate, 2-methacryloylethoxysuccinate, or a combination thereof.

[0170] In some embodiments of the present invention, the total amount of the carboxylic acid-containing vinyl unsaturated monomer (b-1-1) and the other copolymerizable vinyl unsaturated monomer (b-1-2) used in the first alkali-soluble resin (B-1) is 100 parts by weight, and the amount of the carboxylic acid-containing vinyl unsaturated monomer (b-1-1) used is 10 to 90 parts by weight; preferably, the amount of the carboxylic acid-containing vinyl unsaturated monomer (b-1-1) used is 15 to 85 parts by weight; more preferably, the amount of the carboxylic acid-containing vinyl unsaturated monomer (b-1-1) used is 20 to 80 parts by weight.

[0171] The other copolymerizable vinyl unsaturated monomers (b-1-2) can be used alone or in combination, and the other copolymerizable vinyl unsaturated monomers (b-1-2) include, but are not limited to, aromatic vinyl compounds such as styrene (SM), α-methylstyrene, vinyltoluene, p-chlorostyrene, and methoxystyrene; N-phenylmaleimide (PMI), N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, and N-p-hydroxyphenylmaleimide. Maleimides including amines, N-o-methylphenylmaleimide, N-m-methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, and N-cyclohexylmaleimide; methyl acrylate (MA), methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and n-butyl acrylate. 2-Butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate Ester, Allyl Methacrylate, Benzoacrylate, Benzomethacrylate (BzMA), Phenyl Acrylate, Phenyl Methacrylate, Triethylene Glycol Methoxylate, Triethylene Glycol Methoxylate, Dodecyl Methacrylate, Tetradecyl Methacrylate, Hexadecyl Methacrylate, Octadecyl Methacrylate, Eicosyl Methacrylate, Docosyl Methacrylate, Dicyclopentenyloxyethyl Acrylate Unsaturated carboxylic acid esters such as acrylate (DCPOA); N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminopropyl acrylate, N,N-dimethylaminopropyl methacrylate, N,N-dibutylaminopropyl acrylate, and N-iso-butylaminoethyl methacrylate; glycidyl acrylate, glycidyl methacrylate, and other unsaturated carboxylic acid esters; vinyl acetate, vinyl propionate, vinyl butyrate, and other carboxylic acid esters.Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, and methyl allyl glycidyl ether; nitrified vinyl compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylonitrile, N-hydroxyethylacrylonitrile, and N-hydroxyethylmethacrylonitrile; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chlorinated butadiene; or combinations thereof.

[0172] In some embodiments of the present invention, preferably, the other copolymerizable vinyl unsaturated monomers (b-1-2) are styrene, N-phenylmaleimide, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, dicyclopentenyl oxyethyl acrylate, or combinations thereof.

[0173] In some embodiments of the present invention, the total amount of the carboxylic acid-containing vinyl unsaturated monomer (b-1-1) and the other copolymerizable vinyl unsaturated monomer (b-1-2) used in the first alkali-soluble resin (B-1) is 100 parts by weight, and the amount of the other copolymerizable vinyl unsaturated monomer (b-1-2) used is 10 to 90 parts by weight; preferably, the amount of the other copolymerizable vinyl unsaturated monomer (b-1-2) used is 15 to 85 parts by weight; more preferably, the amount of the other copolymerizable vinyl unsaturated monomer (b-1-2) used is 20 to 80 parts by weight.

[0174] There are no particular limitations on the preparation method of the first alkali-soluble resin (B-1), and an appropriate polymerization method can be selected according to requirements. Examples of polymerization methods include solution polymerization. In addition to the required monomer, the reaction solution of the alkali-soluble resin (B) may also include a solvent, an initiator, etc.

[0175] The solvent can be used alone or in combination, and the solvent includes, but is not limited to, (poly)alkylene glycol monoalkyl ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, etc.; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate (propylene glycol methyl ether ether) Acetate (PGMEA), propylene glycol ethyl ether acetate, and other (poly)alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and other ethers; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate (ethyl... Other esters including 3-ethoxypropionate (EEP), ethyl ethoxylate, ethyl hydroxylate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-methoxybutyrate, etc.; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, or N,N-dimethylacetamide, etc. In some embodiments of the present invention, preferably, the solvent is propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, or a combination thereof. The (poly)alkylene glycol monoalkyl ethers refer to either alkylene glycol monoalkyl ethers or polyalkylene glycol monoalkyl ethers. The (poly)alkylene glycol monoalkyl ether acetates refer to either alkylene glycol monoalkyl ether acetates or polyalkylene glycol monoalkyl ether acetates.

[0176] The initiator is generally a free radical polymerization initiator, specifically, for example, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis-2-methylbutyronitrile (AMBN); and peroxide compounds such as benzoyl peroxide.

[0177] The first alkali-soluble resin (B-1) can be used alone or in combination with other resins.

[0178] In some embodiments of the present invention, the polystyrene-converted number-average molecular weight of the first alkali-soluble resin (B-1), as determined by gel permeation chromatography (GPC), is 1,000 to 35,000; preferably, the polystyrene-converted number-average molecular weight is 3,000 to 30,000; more preferably, the polystyrene-converted number-average molecular weight is 5,000 to 25,000.

[0179] In some embodiments of the present invention, based on a total weight of 100 wt% of the solid components of the photosensitive coloring resin composition, the content of the first alkali-soluble resin (B-1) can range from 1 wt% to 60 wt%; preferably, the content of the first alkali-soluble resin (B-1) ranges from 2 wt% to 55 wt%; more preferably, the content of the first alkali-soluble resin (B-1) ranges from 3 wt% to 50 wt%.

[0180] [Second alkali-soluble resin (B-2)]

[0181] The second alkali-soluble resin (B-2) is obtained by polymerizing a mixture, wherein the mixture comprises an epoxy compound (b-2-1) having at least two epoxy groups and a compound (b-2-2) having at least one carboxylic acid group and at least one vinyl unsaturated group. Furthermore, the mixture may selectively comprise a carboxylic anhydride compound (b-2-3) and / or an epoxy-containing compound (b-2-4).

[0182] The epoxy compound (b-2-1) having at least two epoxy groups may have a structure as shown in formula (III-1) or formula (III-2) below. Here, the statement that "the epoxy compound (b-2-1) may have a structure as shown in formula (III-1) or formula (III-2) below" also covers the case where a compound having the structure shown in formula (III-1) and a compound having the structure shown in formula (III-2) below coexist as an epoxy compound (b-2-1). Specifically, the epoxy compound (b-2-1) having at least two epoxy groups is, for example, having a structure as shown in formula (III-1) below.

[0183] (III-1)

[0184] In the above formula (III-1), R 1c R 2c R 3cand R 4c Each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 12 carbon atoms, wherein R 1c The R 2c The R 3c and the R 4c Each can be the same or different.

[0185] The epoxy compound (b-2-1) of formula (III-1) having at least two epoxy groups may include, but is not limited to, an epoxy-containing bisphenol fluorene compound obtained by reacting a bisphenol fluorene compound with an epihalohydrin.

[0186] Specific examples of the bisphenol fluorene-type compounds include, but are not limited to: 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, and 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene. The following are fluorene species: 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, or combinations thereof.

[0187] The epihalohydrin may include, but is not limited to, 3-chloro-1,2-epoxypropane (epichlorohydrin), 3-bromo-1,2-epoxypropane (epibromohydrin), or combinations thereof.

[0188] The epoxy-containing bisphenol fluorene compounds obtained by reacting the aforementioned bisphenol fluorene compounds with the aforementioned halogenated propylene oxide include, but are not limited to: (1) products manufactured by Nippon Steel Chemical Co., Ltd., such as ESF-300; (2) products manufactured by Osaka Gas Co., Ltd., such as PG-100, EG-210; (3) products manufactured by SMS Technology Co., Ltd., such as SMS-F9PhPG, SMS-F9CrG, SMS-F914PG; or combinations thereof.

[0189] Secondly, the epoxy compound (b-2-1) having at least two epoxy groups may also have a structure as shown in the following formula (III-2).

[0190] (III-2)

[0191] In the above formula (III-2), R 5c To R 18c Each of the following independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aromatic group having 6 to 15 carbon atoms, wherein R 5c To the R 18c Each can be the same or different; g represents an integer from 0 to 10.

[0192] The epoxy compound (b-2-1) of formula (III-2) having at least two epoxy groups is obtained, for example, by reacting a compound having the structure shown in formula (III-2-1) with a halopropane in the presence of an alkali metal hydroxide.

[0193] (III-2-1)

[0194] In the above formula (III-2-1), R 5c To R 18c And the definition of g is respectively related to R in equation (III-2). 5c To R 18c The definition of g is the same, so it will not be repeated here.

[0195] Furthermore, the epoxy compound (b-2-1) of formula (III-2) having at least two epoxy groups is, for example, formed by condensing a compound having the structure shown in formula (III-2-2) with a phenol in the presence of an acid catalyst, thereby forming the compound having the structure shown in formula (III-2-1). Then, by adding an excess of halogenated propylene oxide to perform a dehydrohalogenation reaction, the epoxy compound (b-2-1) of formula (III-2) having at least two epoxy groups is obtained.

[0196] (III-2-2)

[0197] In the above formula (III-2-2), R 19c With R 20c Each of the following independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aromatic group having 6 to 15 carbon atoms, and the R 19c With the R 20c Each can be the same or different; T 1 and T 2 Each of these elements independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and the T... 1 and the T 2 Each can be the same or different.

[0198] In some embodiments of the present invention, preferably, the aforementioned halogen atom is chlorine or bromine, the aforementioned alkyl group may be, for example, methyl, ethyl or tert-butyl, and the aforementioned alkoxy group may be, for example, methoxy or ethoxy.

[0199] Specific examples of the phenols mentioned include, but are not limited to, phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, vinylphenol, propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol, or cyclohexylcresol. These phenols can generally be used alone or in combination.

[0200] In some embodiments of the present invention, the amount of the compound having the structure shown in formula (III-2-2) is 1 mole, and the amount of the phenol is from 0.5 moles to 20 moles, preferably from 2 moles to 15 moles.

[0201] Specific examples of the acid catalyst may include, but are not limited to, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. In some embodiments of the present invention, preferably, the acid catalyst is p-toluenesulfonic acid, sulfuric acid, or hydrochloric acid. The acid catalyst may be used alone or in combination.

[0202] In addition, although there is no particular limitation on the amount of acid catalyst used, it is preferable that the amount of acid catalyst used is from 0.1 wt% to 30 wt%, based on the amount of the compound having the structure shown in formula (III-2-2) as described above, which is 100 wt% by weight.

[0203] The condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Specific examples of the organic solvent include, but are not limited to, toluene, xylene, or methylisobutyl ketone. Multiple organic solvents can be used alone or in combination.

[0204] In some embodiments of the present invention, based on a total amount of 100 wt% of the compound having the structure shown in formula (III-2-2) and the phenol, the amount of the organic solvent used is 50 wt% to 300 wt%, preferably 100 wt% to 250 wt%. Furthermore, the operating temperature of the condensation reaction is 40°C to 180°C, and the operating time of the condensation reaction is 1 hour to 8 hours.

[0205] After the condensation reaction is completed, a neutralization or washing process can be performed. The neutralization process adjusts the pH of the post-reaction solution to between pH 3 and pH 7, preferably to between pH 5 and pH 7. The washing process can be performed using a neutralizing agent, which is an alkaline substance, and specific examples include: alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; organic amines such as diethylenetriamine, triethylenetetramine, aniline, and phenylene diamine; and ammonia and sodium dihydrogen phosphate. The washing process can be performed using existing methods, for example, by adding an aqueous solution containing the neutralizing agent to the post-reaction solution and repeatedly extracting. After the neutralization treatment or the water washing treatment, the unreacted phenols and solvents are removed by vacuum heating treatment and then concentrated to obtain the compound having the structure shown in formula (III-2-1).

[0206] Specific examples of the halogenated propylene oxide may include, but are not limited to, 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane, or combinations thereof. Before or during the dehydrohalogenation reaction, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide may be added. The operating temperature of the dehydrohalogenation reaction is between 20°C and 120°C, and the operating time ranges from 1 hour to 10 hours.

[0207] In some embodiments of the present invention, the alkali metal hydroxide added in the dehydrohalogenation reaction may also be an aqueous solution thereof. In a specific example of the present invention, while the aqueous solution of the alkali metal hydroxide is continuously added to the dehydrohalogenation reaction system, water and the propylene oxide halide can be continuously distilled off under reduced pressure or normal pressure, thereby separating and removing water, and the propylene oxide halide can be continuously refluxed back into the reaction system.

[0208] In some embodiments of the present invention, before the dehydrohalogenation reaction, quaternary ammonium salts such as tetramethyl ammonium chloride, tetramethyl ammonium bromide, and trimethyl benzyl ammonium chloride may be added as catalysts, and the reaction is carried out at 50°C to 150°C for 1 to 5 hours. Then, the alkali metal hydroxide or its aqueous solution is added, and the reaction is carried out at 20°C to 120°C for 1 to 10 hours to carry out the dehydrohalogenation reaction.

[0209] In some embodiments of the present invention, based on the total hydroxyl equivalents in the compound having the structure shown in formula (III-2-1) being 1 equivalent, the amount of propylene halide used can be from 1 equivalent to 20 equivalents, preferably from 2 equivalents to 10 equivalents. Based on the total hydroxyl equivalents in the compound having the structure shown in formula (III-2-1) being 1 equivalent, the amount of the alkali metal hydroxide added in the dehydrohalogenation reaction can be from 0.8 equivalents to 15 equivalents, preferably from 0.9 equivalents to 11 equivalents.

[0210] In some embodiments of the present invention, in order to facilitate the dehydrohalogenation reaction, in addition to alcohols such as methanol and ethanol, aprotic polar solvents such as dimethyl sulfone and dimethyl sulfoxide may be added. When using alcohols, based on a total amount of 100 wt% propylene oxide, the amount of alcohol used can be from 2 wt% to 20 wt%, preferably from 4 wt% to 15 wt%. In examples where aprotic polar solvents are used, based on a total amount of 100 wt% propylene oxide, the amount of aprotic polar solvent used can be from 5 wt% to 100 wt%, preferably from 10 wt% to 90 wt%.

[0211] In some embodiments of the present invention, after the dehydrohalogenation reaction is completed, a water washing process may be selectively performed. Subsequently, the halogenated propylene oxide, the alcohol, and the aprotic polar solvent are removed by heating and depressurization. The heating and depressurization are carried out, for example, at a temperature of 110°C to 250°C and a pressure of 1.3 kPa (10 mmHg) or less.

[0212] In some embodiments of the present invention, to avoid the formation of epoxy resin containing hydrolytically decomposable halogens, the solution after the dehydrohalogenation reaction can be added to solvents such as toluene and methyl isobutyl ketone, and then to aqueous solutions of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be added to perform a second dehydrohalogenation reaction. In the dehydrohalogenation reaction, based on the total hydroxyl equivalent in the compound having the structure shown in formula (III-2-1) being 1 equivalent, the amount of alkali metal hydroxide used is 0.01 mol to 0.3 mol, preferably 0.05 mol to 0.2 mol. Furthermore, the operating temperature range of the dehydrohalogenation reaction is 50°C to 120°C, and the operating time range is 0.5 hours to 2 hours.

[0213] After the dehydrohalogenation reaction is completed, salts are removed by filtration and washing. Alternatively, solvents such as toluene and methyl isobutyl ketone can be distilled off by heating under reduced pressure to obtain the epoxy compound (b-2-1) having at least two epoxy groups with the structure shown in formula (III-2). The epoxy compound (b-2-1) having at least two epoxy groups with the structure shown in formula (III-2) may include, but is not limited to, products manufactured by Nippon Kayaku Co. Ltd. under trade names such as NC-3000, NC-3000H, NC-3000S, and NC-3000P.

[0214] The compound (b-2-2) having at least one carboxylic acid group and at least one vinyl unsaturated group is selected, for example, from the group consisting of (1) to (3): (1) acrylic acid, methacrylic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxybutylbutanedioic acid, 2-methacryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxypropylmaleic acid, 2-methacryloyloxybutylmaleic acid, 2-methacryloyloxypropylbutanedioic acid, 2-methacryloyloxypropylbutanedioic acid, 2-methacryloyloxypropylhexahydrophthal ... (1) Oxybutyl phthalic acid, or 2-methacryloyloxybutylhydrophthalic acid; (2) A compound obtained by reacting a hydroxyl-containing (meth)acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound includes, but is not limited to, adipic acid, succinic acid, maleic acid, and phthalic acid; (3) A half-ester compound obtained by reacting a hydroxyl-containing (meth)acrylate with a carboxylic anhydride compound, wherein the hydroxyl-containing (meth)acrylate includes, but is not limited to, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, or pentaerythritol trimethyl acrylate, etc. Furthermore, the carboxylic anhydride compound described herein may be the same as the carboxylic anhydride compound (b-2-3) contained in the mixture of the second alkali-soluble resin (B-2) described below, and therefore will not be described again here.

[0215] The mixture of the second alkali-soluble resin (B-2) may selectively include the carboxylic anhydride compound (b-2-3) and / or the epoxy-containing compound (b-2-4). The carboxylic anhydride compound (b-2-3) may be selected from the group consisting of (1) to (2) below: (1) dicarboxylic anhydride compounds such as butanedioic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl endo-methylene tetrahydrophthalic anhydride, chlorendic anhydride, glutaric anhydride, or 1,3-dioxoisobenzofuran-5-carboxylic anhydride; and (2) benzophenone tetracarboxylic anhydride. dianhydride (BTDA), bisphenyltetracarboxylic dianhydride, or bisphenyl ether tetracarboxylic dianhydride, are tetracarboxylic anhydride compounds.

[0216] The epoxy-containing compound (b-2-4) is, for example, selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, glycidyl ether compounds containing unsaturated groups, unsaturated compounds containing epoxy groups, or any combination thereof. The glycidyl ether compounds containing unsaturated groups include, but are not limited to, compounds under trade names Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192, etc. (all products of Nagase Chemical Industry Co., Ltd.).

[0217] In some embodiments of the present invention, the second alkali-soluble resin (B-2) can be prepared by polymerizing an epoxy compound (b-2-1) having at least two epoxy groups as shown in formula (III-1) with a compound (b-2-2) having at least one carboxylic acid group and at least one vinyl unsaturated group to form a hydroxyl-containing reaction product, followed by adding the carboxylic anhydride compound (b-2-3) for further reaction. Preferably, based on a total hydroxyl equivalent of 1 equivalent in the hydroxyl-containing reaction product, the carboxylic anhydride compound (b-2-3) contains an anhydride group equivalent of 0.4 to 1 equivalent; more preferably, the carboxylic anhydride compound (b-2-3) contains an anhydride group equivalent of 0.75 to 1 equivalent. When multiple carboxylic anhydride compounds (b-2-3) are used, they can be added sequentially or simultaneously during the reaction. When the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound are used as the carboxylic anhydride compound (b-2-3), preferably, the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is 1 / 99 to 90 / 10; more preferably, the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is 5 / 95 to 80 / 20. Furthermore, the operating temperature range of the above reaction is, for example, from 50°C to 130°C.

[0218] In some embodiments of the present invention, the second alkali-soluble resin (B-2) can be prepared by reacting an epoxy compound (b-2-1) having at least two epoxy groups with a structure as shown in formula (III-2) and a compound (b-2-2) having at least one carboxylic acid group and at least one vinyl unsaturated group to form a hydroxyl-containing reaction product, followed by polymerization by adding the carboxylic anhydride compound (b-2-3) and / or the epoxy-containing compound (b-2-4). Based on the total equivalent of epoxy groups on the epoxy compound (b-2-1) having at least two epoxy groups as shown in formula (III-2) being 1 equivalent, preferably, the acid equivalent of the compound (b-2-2) having at least one carboxylic acid group and at least one vinyl unsaturated group is 0.8 equivalents to 1.5 equivalents; more preferably, the acid equivalent of the compound (b-2-2) having at least one carboxylic acid group and at least one vinyl unsaturated group is 0.9 equivalents to 1.1 equivalents. Based on the total amount of hydroxyl groups in the hydroxyl-containing reaction product being 100 mol% (mol%), preferably, the amount of the carboxylic anhydride compound (b-2-3) used is from 10 mol% to 100 mol; more preferably, the amount of the carboxylic anhydride compound (b-2-3) used is from 20 mol% to 100 mol; and most preferably, the amount of the carboxylic anhydride compound (b-2-3) used is from 30 mol% to 100 mol.

[0219] In some embodiments of the present invention, when preparing the second alkali-soluble resin (B-2), an alkaline compound is typically added to the reaction solution as a reaction catalyst to accelerate the reaction. The reaction catalyst can be used alone or in combination, and includes, but is not limited to, triphenylphosphine, triphenyl stibine, triethylamine, triethanolamine, tetramethyl ammonium chloride, and benzyltriethyl ammonium chloride. Based on a total amount of 100 parts by weight of the epoxy compound (b-2-1) having at least two epoxy groups and the compound (b-2-2) having at least one carboxylic acid group and at least one vinyl unsaturated group, preferably, the amount of the reaction catalyst used is from 0.01 parts by weight to 10 parts by weight; more preferably, the amount of the reaction catalyst used is from 0.3 parts by weight to 5 parts by weight.

[0220] In some embodiments of the present invention, a polymerization inhibitor is typically added to the reaction solution to control the degree of polymerization. The polymerization inhibitor may include, but is not limited to, methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol, or phenothiazine. Generally, the polymerization inhibitor may be used alone or in combination. Based on a total amount of 100 parts by weight of the epoxy compound (b-2-1) having at least two epoxy groups and the compound (b-2-2) having at least one carboxylic acid group and at least one vinyl unsaturated group, preferably, the amount of the polymerization inhibitor used is from 0.01 parts by weight to 10 parts by weight; more preferably, the amount of the polymerization inhibitor used is from 0.1 parts by weight to 5 parts by weight.

[0221] In some embodiments of the present invention, a polymerization solvent may be used when preparing the second alkali-soluble resin (B-2). Specific examples of solvents for the polymerization reaction include: alcohols such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, or ethylene glycol; ketones such as methyl ethyl ketone or cyclohexanone; aromatic hydrocarbons such as toluene or xylene; cellosolves such as cellosolve or butyl cellosolve; carbitols such as carbitol or butyl carbitol; propylene glycol monomethyl ethers such as propylene glycol monomethyl ether; polypropylene glycol alkyl ethers such as di(propylene glycol) methyl ether; acetates such as ethyl acetate, butyl acetate, ethylene glycol monooethyl ether acetate, or propylene glycol methyl ether acetate; and ethyl lactate. The solvents used in the polymerization reaction are alkyl lactates such as butyl lactate or butyl lactate; or dialkyl glycol ethers; or ethyl 3-ethoxypropionate. Various solvents can generally be used alone or in combination. Preferably, the acid value of the second base-soluble resin (B-2) is from 50 mg KOH / g to 200 mg KOH / g; more preferably, the acid value of the second base-soluble resin (B-2) is from 60 mg KOH / g to 150 mg KOH / g.

[0222] In some embodiments of the present invention, the number-average molecular weight of the second alkali-soluble resin (B-2) as determined by gel permeation chromatography is 500 to 10,000 based on the polystyrene equivalent; preferably, the number-average molecular weight of the polystyrene equivalent is 800 to 8,000; more preferably, the number-average molecular weight of the polystyrene equivalent is 1,000 to 6,000.

[0223] The second alkali-soluble resin (B-2) can be used alone or in combination with other resins.

[0224] In some embodiments of the present invention, based on a total weight of 100 wt% of the solid components of the photosensitive coloring resin composition, the content of the second alkali-soluble resin (B-2) can range from 1 wt% to 60 wt%; preferably, the content of the second alkali-soluble resin (B-2) ranges from 2 wt% to 55 wt%; more preferably, the content of the second alkali-soluble resin (B-2) ranges from 3 wt% to 50 wt%.

[0225] In some embodiments of the present invention, based on a total weight of 100 wt% of the solid components of the photosensitive coloring resin composition, the content of the alkali-soluble resin (B) ranges from 1 wt% to 60 wt%; preferably, the content of the alkali-soluble resin (B) ranges from 2 wt% to 55 wt%; more preferably, the content of the alkali-soluble resin (B) ranges from 3 wt% to 50 wt%.

[0226] <Photopolymerizable Compounds (C)>

[0227] The photopolymerizable compound (C) may include unsaturated compounds having at least one ethylene unsaturated group and unsaturated compounds having at least two ethylene unsaturated groups.

[0228] Specific examples of unsaturated compounds having at least one ethylene unsaturated group may include, but are not limited to, acrylamide, acrylomorpholine, methacrylomorpholine, 7-amino-3,7-dimethyloctyl acrylate, 7-amino-3,7-dimethyloctyl methacrylate, isobutoxymethacrylamide, isobutoxymethylmethacrylamide, isobornyloxyethyl acrylate, isobornyloxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl methacrylate. Ester, Ethyl diethylene glycol acrylate, Ethyl diethylene glycol methacrylate, Tert-octyl acrylamide, Tert-octyl methacrylamide, Diacetone acrylamide, Diacetone methacrylamide, Dimethylamino acrylate, Dimethylamino methacrylate, Dodecyl acrylate, Dodecyl methacrylate, Dicyclopentenyl acrylate, Dicyclopentenyl methacrylate, Dicyclopentenyl acrylate, Dicyclopentenyl methacrylate, N,N-Dimethylacrylamide, N,N-Dimethylmethacrylamide, Tetrachlorophenyl acrylate, Methacrylic acid Tetrachlorophenyl acrylate, 2-Tetrachlorophenoxyethyl acrylate, 2-Tetrachlorophenoxyethyl methacrylate, Tetrahydrofurfuryl acrylate, Tetrahydrofurfuryl methacrylate, Tetrabromophenyl acrylate, Tetrabromophenyl methacrylate, 2-Tetrabromophenoxyethyl acrylate, 2-Tetrabromophenoxyethyl methacrylate, 2-Trichlorophenoxyethyl acrylate, 2-Trichlorophenoxyethyl methacrylate, Tribromophenyl acrylate, Tribromophenyl methacrylate, 2-Tribromophenoxyethyl acrylate, 2-Tribromophenoxyethyl methacrylate, Acrylic acid 2-Hydroxyethyl acrylate, 2-Hydroxyethyl methacrylate, 2-Hydroxypropyl acrylate, 2-Hydroxypropyl methacrylate, Vinylcaprolactam, N-vinylpiperyl ketone, phenoxyethyl acrylate, phenoxyethyl methacrylate, pentachlorophenyl acrylate, pentachlorophenyl methacrylate, pentabromophenyl acrylate, pentabromophenyl methacrylate, polyethylene monoacrylate, polyethylene monomethacrylate, propylene monoacrylate, polypropylene monomethacrylate, borneol acrylate, borneol methacrylate, or combinations thereof. The unsaturated compounds having at least one vinyl unsaturated group may be used alone or in combination.

[0229] Specific examples of the unsaturated compounds having at least two vinyl unsaturated groups may include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentenyl diacrylate, dicyclopentenyl dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tri(2-hydroxyethyl) isocyanate diacrylate, tri(2-hydroxyethyl) isocyanate dimethacrylate, tri(2-hydroxyethyl) isocyanate triacrylate, tri(2-hydroxyethyl) isocyanate trimethacrylate, caprolactone-modified tri(2-hydroxyethyl) isocyanate triacrylate, and caprolactone-modified tri(2-hydroxyethyl) isocyanate triacrylate. -Hydroxyethyl) isocyanate trimethacrylate, trimethylolpropionic acid triacrylate, trimethylolpropionic acid trimethacrylate, ethylene oxide (hereinafter referred to as EO) modified trimethylolpropionic acid triacrylate, EO modified trimethylolpropionic acid trimethacrylate, propylene oxide (hereinafter referred to as PO) modified trimethylolpropionic acid triacrylate, PO modified trimethylolpropionic acid trimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-Hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, polyester diacrylate, polyester dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipentaerythritol hexaacrylate hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, caprolactone-modified dipentaerythritol hexamethacrylate, caprolactone-modified dipentaerythritol hexamethacrylate, caprolactone-modified dipentaerythritol pentamethacrylate, caprolactone-modified dipentaerythritol pentamethacrylate, di(trimethylolpropionic acid) tetraacrylate, di(trimethylolpropionic acid) tetramethacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol A dimethacrylate, PO-modified bisphenol A diacrylate Bisphenol A diacrylate, PO-modified bisphenol A dimethacrylate, EO-modified hydrogenated bisphenol A diacrylate, EO-modified hydrogenated bisphenol A dimethacrylate, PO-modified hydrogenated bisphenol A diacrylate, PO-modified hydrogenated bisphenol A dimethacrylate, PO-modified glyceryl tripropionate, EO-modified bisphenol F diacrylate, EO-modified bisphenol F dimethacrylate, phenolic polyglycidyl ether acrylate, phenolic polyglycidyl ether methacrylate, products manufactured by Toa Synthetic Co., Ltd. of Japan and designated as TO-1382, or products manufactured by Nippon Kayaku Co., Ltd. and designated as KAYARAD DPCA-12, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, or KAYARAD DPCA-120, etc. The unsaturated compounds having at least two vinyl unsaturated groups can be used alone or in combination.

[0230] In some embodiments of the present invention, preferably, specific examples of the photopolymerizable compound (C) include trimethylolpropionic acid triacrylate, EO-modified trimethylolpropionic acid trimethacrylate, EO-modified trimethylolpropionic acid triacrylate, PO-modified trimethylolpropionic acid triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropionic acid tetraacrylate, PO-modified glyceryl tripropionate, KAYARAD DPCA-12, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120, or combinations thereof.

[0231] In some embodiments of the present invention, more preferably, specific examples of the photopolymerizable compound (C) are dipentaerythritol hexaacrylate, dipentaerythritol tetraacrylate, or combinations thereof.

[0232] The photopolymerizable compound (C) can be used alone or in combination.

[0233] In some embodiments of the present invention, based on a total weight of 100 wt% of the solid components of the photosensitive coloring resin composition, the content of the photopolymerizable compound (C) can range from 5 wt% to 60 wt%; preferably, the content of the photopolymerizable compound (C) ranges from 8 wt% to 55 wt%; more preferably, the content of the photopolymerizable compound (C) ranges from 10 wt% to 50 wt%.

[0234] <Photoinitiator (D)>

[0235] The photoinitiator (D) may be a free radical type photoinitiator.

[0236] The photoinitiator (D) may include acetophenone, biimidazole, acyl oxime, or combinations thereof.

[0237] The acetophenone compounds are selected from p-dimethylamino-acetophenone, α,α'-dimethoxyazoxy-acetophenone, 2,2'-dimethyl-2-phenyl-acetophenone, p-methoxy-acetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N,N-di-methylamino-1-(4-morpholinophenyl)-1-butanone, or combinations thereof.

[0238] The diimidazole compounds are selected from 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-fluorophenyl)-4,4',5,5'-tetraphenyldiimidazole, and 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyldiimidazole. [2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyl-biimidazole [biimidazole], 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole [-biimidazole], 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole, or combinations thereof.

[0239] The acyloxime compounds are selected from ethaneone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-substituted]-, 1-(oxoacetyl oxime)[Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime, for example, the product CGI-242 manufactured by Ciba Specialty Chemicals, with the structure shown in formula (IV-1) below], 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyloxime)[1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyloxime, for example, Ciba Specialty Chemicals] The product CGI-124 manufactured by Chemicals Co., Ltd. has the structure shown in formula (IV-2) below, ethaneone, 1-[9-ethyl-6-(2-chloro-4-benzyl-thio-benzoyl)-9H-carbazole-3-substituted]-, 1-(O-acetyloxime), for example, manufactured by Asahi Denka Co., Ltd., has the structure shown in formula (IV-3) below, or combinations thereof.

[0240] (IV-1)

[0241] (IV-2)

[0242] (IV-3)

[0243] In some embodiments of the present invention, the photoinitiator (D) may further include benzophenone compounds such as thioxanthone, 2,4-diethyl-thioxanthanone, thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone; α-diketone compounds such as benzil and acetyl; acyloin compounds such as benzoin; benzoin methyl ether and benzoin ethyl ether. Keto-ethanol ethers such as ethyl ether and benzoin isopropyl ether; acylphosphine oxides such as 2,4,6-trimethyl-benzoyl-diphenyl-phosphine oxide and bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-benzyl-phosphine oxide; quinones such as anthraquinone and 1,4-naphthoquinone; and benzoylmethyl chloride. Halides of chloride, tribromomethyl-phenylsulfone, tris(trichloromethyl)-s-triazine, etc.; and peroxides of di-tert-butylperoxide, etc. Preferably, the photoinitiator (D) further comprises benzophenone compounds; more preferably, the photoinitiator (D) further comprises 4,4'-bis(diethylamine)benzophenone.

[0244] In some embodiments of the present invention, preferably, the photoinitiator (D) comprises 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime) [e.g., the product CGI-124 manufactured by Ciba Specialty Chemicals].

[0245] The photoinitiator (D) can be used alone or in combination with other agents.

[0246] In some embodiments of the present invention, based on a total weight of 100 wt% of the solid components of the photosensitive coloring resin composition, the content of the photoinitiator (D) can range from 0.1 wt% to 15 wt%; preferably, the content of the photoinitiator (D) ranges from 0.5 wt% to 13 wt%; more preferably, the content of the photoinitiator (D) ranges from 1 wt% to 10 wt%.

[0247] <Solvent (E)>

[0248] The preparation of the photosensitive coloring resin composition typically involves first dissolving all components except the colorant (A) in the solvent (E) to form a liquid composition, and then adding the colorant (A) and mixing thoroughly. The solvent (E) must be selected to dissolve the alkali-soluble resin (B), the photopolymerizable compound (C), and the photoinitiator (D), and must not react with these components and possess appropriate volatility. Furthermore, when the additive (F) is added, the solvent (E) must be selected to dissolve the additive (F), and must not react with these components and possess appropriate volatility.

[0249] Furthermore, the solvent (E) may be the same as the solvent used to prepare the alkali-soluble resin (B), and will not be described again here. Also, the solvent (E) may be used alone or in combination. In some embodiments of the present invention, preferably, the solvent (E) includes propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, or a combination thereof.

[0250] In some embodiments of the present invention, based on a total weight of 100 wt% of the photosensitive coloring resin composition, the content of the solvent (E) can range from 55 wt% to 95 wt%; preferably, the content of the solvent (E) ranges from 60 wt% to 95 wt%; more preferably, the content of the solvent (E) ranges from 70 wt% to 95 wt%.

[0251] <Additives (F)>

[0252] In some embodiments of the present invention, the photosensitive coloring resin composition further includes an additive (F), such as a filler, a polymeric compound other than the alkali-soluble resin (B), an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-agglomeration agent, etc.

[0253] The filler may include glass, aluminum, or combinations thereof.

[0254] Examples of the polymeric compounds include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroacrylate, or combinations thereof.

[0255] The adhesion promoter may include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-epoxypropanolpropyltrimethoxysilane, 3-epoxypropanolpropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methpropenoloxypropyltrimethoxysilane, 3-thiolpropyltrimethoxysilane, or combinations thereof.

[0256] Examples of antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or combinations thereof.

[0257] Examples of ultraviolet absorbers include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxyphenyl ketone, or combinations thereof.

[0258] Examples of anti-agglomerating agents include sodium polyacrylate.

[0259] In some embodiments of the present invention, in order to precisely control the nickel content, the additive (F) may selectively use nickel-containing additives, including but not limited to nickel dichloride (NiCl2), nickel acetylacetonate [Ni(acac)2], and nickel sulfate (NiSO4).

[0260] In some embodiments of the present invention, in order to precisely control the calcium content, the additive (F) may selectively use calcium-containing additives, including but not limited to calcium chloride (CaCl2), calcium acetylacetonate [Ca(acac)2], calcium carbonate (CaCO3), and calcium nitrate [Ca(NO3)2].

[0261] The additive (F) can be used alone or in combination.

[0262] In some embodiments of the present invention, preferably, the additive (F) is 3-thiol-propyltrimethoxysilane, 2,2-thiobis(4-methyl-6-tert-butylphenol), or a combination thereof.

[0263] In some embodiments of the present invention, based on a total weight of 100 wt% of the photosensitive coloring resin composition, the content of the additive (F) may be greater than 0 wt% and less than 10 wt%; preferably, the content of the additive (F) is greater than 0 wt% and less than 7 wt%; more preferably, the content of the additive (F) is greater than 0 wt% and less than 5 wt%.

[0264] Preparation method of photosensitive coloring resin composition

[0265] There are no particular limitations on the preparation method of the photosensitive coloring resin composition. Specifically, the preparation method of the photosensitive coloring resin composition can be exemplified by: (1) firstly, adding the colorant (A) to the solvent (E) to prepare a colorant dispersion, and then adding and mixing the alkali-soluble resin (B), the photopolymerizable compound (C), the photoinitiator (D), and the additive (F) as needed to the colorant dispersion; (2) simultaneously adding and mixing the colorant (A), the alkali-soluble resin (B), the photopolymerizable compound (C), the photoinitiator (D), and the additive (F) as needed to the solvent (E); (3) First, a method in which the alkali-soluble resin (B), the photopolymerizable compound (C), the photoinitiator (D), and the additive (F) as needed are added to the solvent (E) and mixed, and then the colorant (A) is added and dispersed; and (4) a method in which the colorant (A) and a portion of the alkali-soluble resin (B) are added to the solvent (E) to prepare a colorant dispersion, and then another portion of the alkali-soluble resin (B), the photopolymerizable compound (C), the photoinitiator (D), and the additive (F) as needed are added to the colorant dispersion and mixed, etc.

[0266] In view of effectively preventing colorant aggregation and uniform dispersion, the photosensitive coloring resin composition is preferably prepared by the methods described in (1) and (4) above.

[0267] Methods for uniformly dispersing / mixing the components include using a mixer and / or a disperser for mixing and / or dispersion. Dispersors may include roller mills such as two-roll mills and three-roll mills, ball mills, vibratory ball mills, paint conditioners, continuous disc bead mills, and continuous ring bead mills. Preferably, the dispersion conditions of the bead mill are that the bead diameter used is from 0.03 mm to 2.00 mm; more preferably, the dispersion conditions of the bead mill are that the bead diameter used is from 0.10 mm to 1.0 mm.

[0268] On the other hand, the nickel and calcium in the photosensitive coloring resin composition can be introduced along with the raw materials such as the colorant (A) and the solvent (E). The nickel and calcium can also be incorporated into the raw materials through a device used for stirring, mixing, and dispersing. Since the amount of nickel and calcium introduced from the colorant (A) is relatively large, in some embodiments of the present invention, it is preferable that the content of the nickel and calcium is controlled by the colorant (A).

[0269] In some embodiments of the present invention, the content of nickel and calcium in the colorant (A) can be controlled by washing the colorant (A) with a liquid including, but not limited to, alcohols and water. Preferably, considering manufacturing costs, the colorant (A) is washed with water. The washing process may include, but is not limited to, suspending the colorant (A) in water and then washing the suspended colorant (A) in batches, or continuously washing the suspended colorant (A) with running water. Specifically, the batch washing utilizes a filter press; a homogenizer such as a high-pressure homogenizer, a low-pressure homogenizer, or an ultrasonic homogenizer; or a mixer such as a sand mill, a ball mill, a roller mill, or a magnetic stirrer to disperse and wash the colorant (A) suspended in water. The continuous washing utilizes equipment such as a vacuum filter, a belt press, a centrifuge, or a cloth funnel to continuously supply deionized water to the colorant (A), thereby continuously washing the colorant (A).

[0270] More specifically, the method of controlling the content of nickel and calcium in the colorant (A) through the water washing process includes, for example: using deionized water to wash the colorant (A) to avoid the nickel and calcium present in the water affecting the content of nickel and calcium; adjusting the number of water washes in the batch washing process; adjusting the relative amount of water and colorant (A) in the water washing process; adjusting the temperature of the water washing process; adjusting the pH value of the water washing process; optimizing the agitator of the water washing process; and adjusting the time of the water washing process.

[0271] In some embodiments of the present invention, in order to effectively adjust the content of nickel and calcium in the colorant (A), preferably, the washing process can be selected from adjusting the number of washes during the batch washing, continuously washing the colorant (A) with running water, adjusting the temperature of the washing process, etc. In some embodiments of the present invention, the temperature range of the washing process is 20°C to 80°C; preferably, the temperature range of the washing process is 30°C to 70°C; more preferably, the temperature range of the washing process is 40°C to 60°C.

[0272] In some embodiments of the present invention, when the colorant (A) is continuously washed with running water, the amount of running water used ranges from 30 parts by weight to 40,000 parts by weight, based on 1 part by weight of the colorant (A); preferably, the amount of running water used ranges from 40 parts by weight to 20,000 parts by weight; more preferably, the amount of running water used ranges from 50 parts by weight to 10,000 parts by weight; and most preferably, the amount of running water used ranges from 60 parts by weight to 5,000 parts by weight.

[0273] In some embodiments of the present invention, the deionized water used for the water washing treatment is obtained, for example but not limited to, by treating the raw water with at least one of a treatment agent selected from strong or weak acid cation exchange resin, strong or weak base anion exchange resin, ion exchange membrane, chelate resin, activated carbon, antibacterial activated carbon, etc.; preferably, the raw water is treated with a combination of two or more of the above treatment agents, and then subjected to steps such as depressurization and distillation to obtain the deionized water.

[0274] In some embodiments of the present invention, in order to further precisely adjust the content of nickel and calcium in the colorant (A), preferably, the apparatus used for the water washing process is a homogenizer such as a high-pressure homogenizer, a low-pressure homogenizer, or an ultrasonic homogenizer; more preferably, in terms of cost reduction, the apparatus used for the water washing process is an ultrasonic homogenizer.

[0275] In some embodiments of the present invention, the washing process is performed in batches to allow for more precise adjustment of the nickel and calcium content in the colorant (A). Specifically, the batch washing involves washing out impurities such as nickel and calcium metal salts, free metals, and other inorganic salts from the colorant (A) into water in which the colorant (A) is suspended, filtering the water to remove the impurities by removing the filtrate, then resuspending the wet filter cake of the colorant (A) in water, and repeating the above processing steps as needed to adjust the nickel and calcium content in the colorant (A) to a suitable range. Finally, the wet filter cake of the colorant (A) is dried to obtain the colorant (A) used to prepare the photosensitive coloring resin composition. In some embodiments of the present invention, in terms of the effectiveness and cost of the water washing treatment, preferably, the number of water washing treatments is 2 to 50 times; more preferably, the number of water washing treatments is 3 to 40 times; particularly preferably, the number of water washing treatments is 4 to 30 times; and even more preferably, the number of water washing treatments is 5 to 20 times.

[0276] In some embodiments of the present invention, the amount of water used for the batch washing ranges from 30 parts by weight to 40,000 parts by weight, based on 1 part by weight of the colorant (A); preferably, the amount of water used for the batch washing ranges from 40 parts by weight to 20,000 parts by weight; more preferably, the amount of water used for the batch washing ranges from 50 parts by weight to 10,000 parts by weight; particularly preferably, the amount of water used for the batch washing ranges from 60 parts by weight to 5,000 parts by weight.

[0277] Color filters and their manufacturing methods

[0278] This invention also provides a method for manufacturing a color filter, and a color filter obtained by the method. The method for manufacturing the color filter includes forming a pixel layer using a photosensitive coloring resin composition as described above. Specifically, the photosensitive coloring resin composition, mixed in a solution state, is coated onto a substrate using coating methods such as rotary coating, cast coating, inkjet coating, or roller coating. After coating, most of the solvent is removed by vacuum drying, and then the solvent is removed by pre-bake to form a pre-baked coating. The conditions for vacuum drying and pre-baking vary depending on the type and ratio of the components. Typically, vacuum drying is performed at a pressure of 0 mmHg to 200 mmHg for 1 to 60 seconds, and pre-baking is performed at a temperature of 70°C to 110°C for 1 to 15 minutes. After the pre-baking, the pre-baked coating is exposed under a specified photomask and then immersed in a developing solution at 23±2°C for 15 seconds to 5 minutes to remove unwanted portions and form a pixel layer. The light used for exposure is preferably ultraviolet light such as g-line, h-line, or i-line, and the ultraviolet light device can be a (ultra) high-pressure mercury lamp or a metal halide lamp.

[0279] Specific examples of the substrate include: alkali-free glass, soda-lime glass, hard glass (Pyles glass), quartz glass, sodium glass, or a substrate with a transparent conductive film attached to the glass used in liquid crystal display devices; or a substrate for photoelectric conversion devices such as solid-state imaging devices (e.g., silicon substrate). The substrate typically first forms a black matrix that isolates each pixel layer.

[0280] Furthermore, specific examples of the developing solution include, for instance, an alkaline aqueous solution composed of at least one of the following alkaline compounds: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methylsilicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, wherein the concentration of the alkaline compound in the alkaline aqueous solution is generally from 0.001 wt% to 10 wt%; preferably, the concentration of the alkaline compound in the alkaline aqueous solution is from 0.005 wt% to 5 wt%; more preferably, the concentration of the alkaline compound in the alkaline aqueous solution is from 0.01 wt% to 1 wt%.

[0281] When using the developer solution composed of the alkaline aqueous solution, the pre-baked coating with the pattern is generally washed with water after development, and then the pixel layer is formed by air drying with compressed air or compressed nitrogen.

[0282] After air drying, the substrate with the pixel layer is heated at 100°C to 280°C for 1 to 15 minutes using a heating device such as a hot plate or oven to remove volatile components from the pixel layer and to induce a thermosetting reaction in the unreacted vinyl unsaturated double bonds in the pixel layer. The same steps are repeated three times on predetermined pixels using photosensitive coloring resin compositions of various colors (mainly red, green, and blue) to obtain red, green, and blue pixel layers.

[0283] Secondly, an ITO (indium tin oxide) vapor-deposited film is formed on the pixel layer under vacuum at a temperature of 220°C to 250°C. If necessary, the ITO vapor-deposited film is etched and wired, and then polyimide for liquid crystal alignment is coated on it. After heat treatment, it can be used as a color filter for liquid crystal displays.

[0284] Furthermore, the aforementioned liquid crystal alignment film is used to restrict the alignment of liquid crystal molecules. It is not specifically limited here; any inorganic or organic material can be used. The technology for forming the liquid crystal alignment film is well known to those skilled in the art and is not the focus of this invention, so it will not be described further.

[0285] Liquid Crystal Displays

[0286] The present invention also provides a liquid crystal display (LCD) comprising a color filter substrate containing a color filter manufactured using the method described above; and a driving substrate having a thin-film transistor (TFT). The LCD is configured with the color filter substrate and the driving substrate facing each other, with a gap (cell gap) inserted between them. A sealant is applied around the opposing surfaces of the color filter substrate and the driving substrate, and liquid crystal is injected into the gap defined by the sealant and the opposing surfaces of the color filter substrate and the driving substrate, sealing the injection hole to form a liquid crystal cell. Then, a polarizing plate is attached to the outer surface of the liquid crystal cell, i.e., to the other sides of each substrate constituting the liquid crystal cell, to obtain the LCD.

[0287] As for the liquid crystals used above, that is, liquid crystal compounds or liquid crystal compositions, there is no particular limitation here, but any kind of liquid crystal compound and liquid crystal composition can be used.

[0288] The present invention will be further described with reference to the following embodiments, but it should be understood that these embodiments are for illustrative purposes only and should not be construed as limiting the implementation of the present invention.

[0289] [Synthetic Example B-1] First base soluble resin

[0290] One part by weight of 2,2'-azobisisobutyronitrile, 240 parts by weight of propylene glycol methyl ether acetate, 20 parts by weight of methacrylic acid, 15 parts by weight of styrene, 35 parts by weight of benzyl methacrylate, and 30 parts by weight of N-phenylmaleimide were placed in a round-bottom flask equipped with a stirrer and a condenser. The flask was filled with nitrogen gas. The mixture was then slowly stirred and heated to 80°C to allow the reactants to mix uniformly and polymerize for 4 hours. Afterward, the temperature was raised to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile was added. After polymerizing for 1 hour, the first alkali-soluble resin (B-1) of Synthetic Example B-1 was obtained.

[0291] [Synthetic Example B-2] First base soluble resin

[0292] Two parts by weight of 2,2'-azobisisobutyronitrile, 300 parts by weight of dipropylene glycol methyl ether, 15 parts by weight of methacrylic acid, 15 parts by weight of 2-hydroxyethyl acrylate, and 70 parts by weight of benzyl methacrylate were placed in a round-bottom flask equipped with a stirrer and a condenser. The flask was filled with nitrogen gas. The mixture was then slowly stirred and heated to 80°C to ensure uniform mixing of the reactants, and polymerization was carried out for 3 hours. Afterward, the temperature was raised to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile was added. Polymerization was carried out for 1 hour to obtain the first alkali-soluble resin (B-1) of Synthetic Example B-2.

[0293] [Example 1] Photosensitive coloring resin composition

[0294] First, 32.5 parts by weight of compound (22) [i.e., colorant (A-1-1)] and 2500 parts by weight of deionized water were placed in a wide-mouth bottle to obtain a liquid to be treated. The colorant (A-1-1) suspended in the deionized water in the liquid to be treated was subjected to a first water washing treatment at 30°C in a batch washing manner. Then, the liquid to be treated was filtered to obtain a wet filter cake containing the colorant (A-1-1). The wet filter cake was mixed with 2500 parts by weight of deionized water to suspend the colorant (A-1-1) in the deionized water to obtain another solution to be treated. Then, the above steps were repeated to perform water washing treatment in a batch washing manner until the 10th water washing treatment was completed to obtain the purified colorant (A-1-1). Each water washing process involves stirring with an ultrasonic homogenizer for 10 minutes and filtering with filter paper (brand: ADVANTEC, trade name: FILTER PAPER QUANTITATIVE ASHLESS, specification: No. 5C, 150mm).

[0295] Then, in another wide-mouth bottle, 32.5 parts by weight of the refined colorant (A-1-1), 400 parts by weight of propylene glycol methyl ether acetate (PGMEA, manufactured by Daicel-Allnex, i.e., solvent (E-1)), and 2.0 parts by weight of zirconia beads with a particle size of 2 mm were placed. After pre-pulverizing using a paint shaker (PCMH-C50M, manufactured by Asada Tetsugang) for 1 hour, the solution in the wide-mouth bottle was transferred to another wide-mouth bottle, and 2.0 parts by weight of zirconia beads with a particle size of 0.1 mm were added. The solution was then shaken using a paint shaker for 20 hours to obtain the colorant dispersion of Example 1.

[0296] Next, 432.5 parts by weight of the colorant dispersion [containing 32.5 parts by weight of the colorant (A-1-1)], 45 parts by weight of the first alkali-soluble resin of Synthetic Example B-1 [i.e., alkali-soluble resin (B-1)], 20 parts by weight of dipentaerythritol hexaacrylate [i.e., photopolymerizable compound (C-1)], 2.5 parts by weight of 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime) [i.e., photoinitiator (D-1)], 0.043 parts by weight of nickel dichloride, and 0.018 parts by weight of calcium chloride were added to a mixed solvent containing 100 parts by weight of propylene glycol methyl ether acetate [i.e., solvent (E-1)] and 100 parts by weight of ethyl 3-ethoxypropionate [i.e., solvent (E-2)], and stirred with a shaking stirrer. After being thoroughly stirred with a stirrer, the photosensitive coloring resin composition of Example 1 can be obtained.

[0297] [Examples 2 to 10 and Comparative Examples 1 to 2] Photosensitive coloring resin composition

[0298] The photosensitive coloring resin compositions of Examples 2 to 10 and Comparative Examples 1 to 2 were prepared in a manner similar to that of Example 1, except that the washing conditions, the types of components in the photosensitive coloring resin compositions, and their amounts were changed. The washing conditions of Examples 2 to 10 and Comparative Examples 1 to 2 are shown in Table 1, the specific compositions are shown in Tables 2 and 3, and the corresponding components in Tables 2 and 3 are shown in Table 4.

[0299] [Evaluation Items]

[0300] The following description uses the photosensitive coloring resin composition of Example 1 as an example. The other photosensitive coloring resin compositions of Examples 2 to 10 and Comparative Examples 1 to 2 were carried out in the same manner.

[0301] Nickel and calcium content in the photosensitive coloring resin composition: Approximately 0.2 g of the photosensitive coloring resin composition of Example 1 was weighed and subjected to microwave pressure-sealed decomposition using a microwave digestion apparatus (Anton Paar, Model: Multiwave 7000) and nitric acid to obtain the sample to be tested. The sample to be tested was analyzed using an inductively coupled plasma mass spectrometer (ICP-MS, Thermo Fisher Scientific, Model: ELEMENT2) to obtain the nickel (Ni) and calcium (Ca) content in the photosensitive coloring resin composition of Example 1.

[0302] Size of foreign matter after multi-stage thermal processing: The photosensitive coloring resin composition of Example 1 was spin-coated onto a glass substrate (Eagle 2000 manufactured by Corning) with dimensions of 100mm × 100mm and a thickness of 0.7mm. The coating conditions were adjusted so that the thickness of the coating film formed after drying of the photosensitive coloring resin composition of Example 1 reached 2.0μm. After coating, the coating film was pre-baked on a heating plate at 100°C for 2 minutes to obtain a pre-baked coating film. Then, an exposure machine (brand: Canon, model: PLA-501F) was used with an irradiation energy of 50mJ / cm². 2 The pre-baked coating was irradiated with ultraviolet light. After exposure, the exposed pre-baked coating was immersed in a developer at 23°C for 2 minutes for development, followed by rinsing with pure water. It was then post-baked at 230°C for 80 minutes and cooled at 25°C for 30 minutes. The post-baking and cooling processes were repeated 10 times each to complete the multi-stage thermal processing and obtain the sample film for testing.

[0303] Foreign matter on the surface of the sample film was observed using an optical microscope to obtain the size of the foreign matter after the multi-stage thermal processing. Smaller foreign matter size after the multi-stage thermal processing is preferred. The evaluation criteria are as follows:

[0304] ◎: The size of foreign matter after multi-stage thermal processing is <2μm;

[0305] ○: 2μm ≤ size of foreign matter after multi-stage thermal processing < 4μm;

[0306] △: The size of foreign matter after multi-stage thermal processing is less than 6μm, ≤ 4μm;

[0307] ×: The size of foreign matter after multi-stage thermal processing is ≥6μm.

[0308] Table 1

[0309]

[0310] Table 2

[0311]

[0312] Table 3

[0313]

[0314] Table 4

[0315]

[0316]

[0317] Referring to Tables 2 and 3, the photosensitive coloring resin compositions of Examples 1 to 10 employ the colorant (A) including the triphenylmethane-based colorant (A-1) and simultaneously control the nickel content within the range of 1 ppm to 100 ppm. Therefore, the size of the foreign matter in the test sample film formed by the photosensitive coloring resin compositions of Examples 1 to 10 after the multi-stage thermal process is less than 6 μm, thus exhibiting a small size of foreign matter after the multi-stage thermal process.

[0318] Furthermore, the photosensitive coloring resin compositions of Examples 1 to 6 and 8 to 10, by controlling the nickel content within the range of 3 ppm to 50 ppm, result in foreign matter sizes in the test sample films formed using these compositions being less than 4 μm after the multi-stage thermal processing, thus exhibiting smaller foreign matter sizes. Even further, the photosensitive coloring resin compositions of Examples 1 to 3 and 8 to 10, by controlling the nickel content within the range of 3 ppm to 50 ppm and simultaneously controlling the calcium content within the range of 5 ppm to 50 ppm, result in foreign matter sizes in the test sample films formed using these compositions being less than 2 μm after the multi-stage thermal processing, thus exhibiting even smaller foreign matter sizes.

[0319] On the other hand, the triphenylmethane-based colorant (A-1) used in the photosensitive coloring resin compositions of Examples 1 to 6 and 8 to 10 all include heterogeneous multiple acid anions containing at least one of molybdenum and tungsten. Therefore, the size of foreign matter in the test sample film formed by the photosensitive coloring resin compositions of Examples 1 to 6 and 8 to 10 after the multi-stage thermal process is less than 4 μm, thus having a small size of foreign matter after the multi-stage thermal process.

[0320] Referring to Table 3, in contrast to Comparative Examples 1 and 2, the colorant (A) used in the photosensitive coloring resin composition of Comparative Example 1 was not subjected to water washing treatment to control the nickel content, resulting in an excessively high nickel content in the photosensitive coloring resin composition of Comparative Example 1 (greater than 100 ppm). This resulted in the size of foreign matter after the multi-stage thermal processing in the test sample film formed by the photosensitive coloring resin composition of Comparative Example 1 being 6 μm or more, indicating a large size of foreign matter after the multi-stage thermal processing. In contrast, the colorant (A) used in the photosensitive coloring resin composition of Comparative Example 2 had too much nickel removed by the water washing treatment, resulting in an excessively low nickel content in the photosensitive coloring resin composition of Comparative Example 2 (less than 1 ppm). This resulted in the size of foreign matter after the multi-stage thermal processing in the test sample film formed by the photosensitive coloring resin composition of Comparative Example 2 being 6 μm or more, indicating a large size of foreign matter after the multi-stage thermal processing.

[0321] In summary, the photosensitive coloring resin composition of the present invention uses the colorant (A) including the triphenylmethane-based colorant (A-1), and simultaneously controls the nickel content in the photosensitive coloring resin composition within the range of 1 ppm to 100 ppm. Therefore, the film formed by the photosensitive coloring resin composition has small-sized multi-stage post-thermal processing foreign matter, thereby enabling the photosensitive coloring resin composition to be further used to prepare a pixel layer. Consequently, when the pixel layer is applied to prepare color filters and liquid crystal displays, it can meet the requirements of high-resolution displays, thus effectively achieving the purpose of the present invention.

[0322] However, the above description is merely an embodiment of the present invention and should not be construed as limiting the scope of the present invention. Any simple equivalent changes and modifications made in accordance with the claims and description of the present invention shall still fall within the scope of the patent of the present invention.

Claims

1. A photosensitive coloring resin composition, characterized in that: The photosensitive coloring resin composition comprises: Colorant (A); Alkali-soluble resin (B); Photopolymerizable compound (C); Photoinitiator (D); and Solvent (E); The nickel content in the photosensitive coloring resin composition ranges from 1 ppm to 100 ppm, and the colorant (A) includes a triphenylmethane-based colorant (A-1).

2. The photosensitive coloring resin composition according to claim 1, characterized in that: The nickel content in the photosensitive coloring resin composition ranges from 2 ppm to 80 ppm.

3. The photosensitive coloring resin composition according to claim 1, characterized in that: The nickel content in the photosensitive coloring resin composition ranges from 3 ppm to 50 ppm.

4. The photosensitive coloring resin composition according to claim 1, characterized in that: The calcium content in the photosensitive coloring resin composition ranges from 1 ppm to 100 ppm.

5. The photosensitive coloring resin composition according to claim 1, characterized in that: The calcium content in the photosensitive coloring resin composition ranges from 5 ppm to 50 ppm.

6. The photosensitive coloring resin composition according to claim 1, characterized in that: The triphenylmethane-based colorant (A-1) comprises a triphenylmethane-based colorant having a structure as shown in formula (I-1-1). (I-1-1) In equation (I-1-1), A represents an organic group with a p-valence, wherein the carbon atom in the organic group directly bonded to N does not have a π bond; the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group; the carbon chain of the aliphatic hydrocarbon group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom; the carbon chain of the aromatic group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom. R 1 R 2 R 3 R 4 and R 5 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, R 2 With R 3 They can bond together to form a ring structure, R 4 With R 5 They can bond together to form a ring structure, multiple R 1 R 2 R 3 R 4 and R 5 Each can be the same or different. Ar 1 Indicates substituted or unsubstituted divalent aromatic groups, multiple Ar 1 Each can be the same or different. B q- Indicates anion. p represents an integer greater than or equal to 1. r and s each independently represent integers greater than 1.

7. The photosensitive coloring resin composition according to claim 6, characterized in that: The B q- It is a heterogeneous multiple acid anion containing at least one of molybdenum and tungsten.

8. A method for manufacturing a color filter, characterized in that: The method for manufacturing the color filter comprises: forming a pixel layer using a photosensitive coloring resin composition as described in any one of claims 1 to 7.

9. A color filter, characterized in that: The color filter is manufactured by the method for manufacturing a color filter as described in claim 8.

10. A liquid crystal display, characterized in that: The liquid crystal display includes: the color filter as described in claim 9.

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