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

Abstract

A 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 iodine value range of the photosensitive colored resin composition is 0.5 g / 100g to 15g / 100g, and the coloring agent (A) comprises a zinc phthalocyanine dye (A-1). The invention also provides a manufacturing method of a color filter using the photosensitive colored resin composition to form a pixel layer, a color filter manufactured by the manufacturing method, and a liquid crystal display comprising the color filter. By adopting the coloring agent (A) containing the zinc phthalocyanine dye (A-1) and controlling the iodine value range of the photosensitive colored resin composition to be 0.5 g / 100g to 15g / 100g, the size of foreign matters in a pixel layer formed by the photosensitive colored resin composition after a multi-stage thermal process can be reduced.

Description

Technical Field

[0001] This invention relates to a resin composition, a color filter, a method for manufacturing the same, and a liquid crystal display, 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), the manufacturing process of color filters is 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 lead to crystallization or aggregation of the photosensitive coloring resin composition, resulting in foreign matter. Excessively large foreign matter sizes in the pixel layer can cause serious defects in displays with high pixel density (Pixel Per Inch, PPI).

[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 iodine value of the photosensitive coloring resin composition ranges from 0.5 g / 100 g to 15 g / 100 g, and the colorant (A) includes zinc phthalocyanine dye (A-1).

[0009] In the photosensitive coloring resin composition of the present invention, the iodine value of the photosensitive coloring resin composition ranges from 0.7 g / 100 g to 10 g / 100 g.

[0010] In the photosensitive coloring resin composition of the present invention, the iodine value of the photosensitive coloring resin composition ranges from 0.9 g / 100 g to 5 g / 100 g.

[0011] In the photosensitive coloring resin composition of the present invention, the zinc phthalocyanine dye (A-1) is a compound as shown in formula (I).

[0012] (I)

[0013] In the above formula (I), A 1 To A 16 Each independently represents a hydrogen atom, a halogen atom, or a group as shown in formula (II), and A 1 To the A 16 At least one of them represents the group shown in formula (II),

[0014] (II)

[0015] In formula (II), X represents a divalent linking group, and A 17 Indicates substituted or unsubstituted phenyl groups. Indicates the location of the bond.

[0016] In the photosensitive coloring resin composition of the present invention, A 1 To the A 16 Six or more in the character represent fluorine atoms.

[0017] In the photosensitive coloring resin composition of the present invention, A 17 It represents 4-alkoxycarbonylphenyl.

[0018] In the photosensitive coloring resin composition 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) ranges from 5 wt% to 80 wt%, the content of the zinc phthalocyanine dye (A-1) ranges from 5 wt% to 80 wt%, the content of the alkali-soluble resin (B) ranges from 5 wt% to 60 wt%, the content of the photopolymerizable compound (C) ranges from 5 wt% to 50 wt%, and the content of the photoinitiator (D) ranges from 0.1 wt% to 12 wt%; based on a total weight of 100 wt% of the photosensitive coloring resin composition, the content of the solvent (E) ranges from 55 wt% to 95 wt%.

[0019] A second objective of this invention is to provide a method for manufacturing a color filter.

[0020] The method for manufacturing a color filter of the present invention includes forming a pixel layer using the photosensitive coloring resin composition described above.

[0021] A third objective of this invention is to provide a color filter.

[0022] The color filter of the present invention is manufactured by the color filter manufacturing method described above.

[0023] The fourth objective of this invention is to provide a liquid crystal display.

[0024] The liquid crystal display of the present invention includes the color filter as described above.

[0025] The beneficial effects of the present invention are as follows: by using the colorant (A) including zinc phthalocyanine dye (A-1) and simultaneously controlling the iodine value of the photosensitive coloring resin composition to be between 0.5g / 100g and 15g / 100g, the photosensitive coloring resin composition can reduce the size of foreign matter after multi-stage thermal processing in the formed pixel layer, thereby enabling the pixel layer to be applied in color filters and liquid crystal displays to meet the requirements of high-resolution displays. Detailed Implementation

[0026] 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 thermal process conditions, the photosensitive coloring resin compositions in the pixel layer are prone to crystallization or local aggregation, forming micron-sized particles, thus increasing the size of foreign matter. Therefore, fabricating color filters using pixel layers containing excessively large foreign matter generated by multi-stage high-temperature processes 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 "foreign matter after multi-stage thermal processing") generated in the pixel layer by controlling the iodine value range of the photosensitive coloring resin composition to 0.5g / 100g to 15g / 100g and using a colorant (A) including zinc phthalocyanine dye (A-1).

[0027] Photosensitive coloring resin composition

[0028] 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 iodine value of the photosensitive coloring resin composition ranges from 0.5 g / 100 g to 15 g / 100 g, and the colorant (A) comprises zinc phthalocyanine dye (A-1). Furthermore, in some embodiments of this invention, the photosensitive coloring resin composition may selectively include an additive (F).

[0029] In this document, "iodine value" refers to the amount of halogen bound to 100g of the photosensitive coloring resin composition, and the amount of halogen is converted into grams of iodine.

[0030] In some embodiments of the present invention, in order to further reduce 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, preferably, the iodine value of the photosensitive coloring resin composition is in the range of 0.7 g / 100 g to 10 g / 100 g; more preferably, the iodine value of the photosensitive coloring resin composition is in the range of 0.9 g / 100 g to 5 g / 100 g.

[0031] In this invention, if the iodine value of the photosensitive coloring resin composition does not fall within the range of 0.5g / 100g to 15g / 100g, 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.

[0032] It should be noted that although the detailed mechanism by which the iodine value of the aforementioned photosensitive coloring resin composition falls outside the range of 0.5 g / 100 g to 15 g / 100 g, 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, the following factors are speculated: When the iodine value of the photosensitive coloring resin composition is too high, it indicates an increase in the proportion of unsaturated groups in the photosensitive coloring resin composition, leading to an excessively high content of aliphatic long chains in the pixel layer obtained after exposure. These aliphatic segments have a large difference in interfacial energy at the molecular level with the aromatic planar structure of the zinc phthalocyanine dye (A-1), making it difficult to form a stable dispersion. Therefore, during multi-stage thermal processing, these aliphatic segments undergo local phase separation due to thermal motion and oxidation, further promoting the aggregation or precipitation of the zinc phthalocyanine dye (A-1) to form particulate foreign matter.

[0033] Furthermore, this invention conducted research to gain a deeper understanding of foreign matter formation in the pixel layer. The results showed that the iodine value of the photosensitive coloring resin composition must be controlled within a specific low range. When the iodine value of the photosensitive coloring resin composition is less than 0.5 g / 100 g, it indicates insufficient crosslinking density, suggesting the presence of low-molecular-weight substances. These low-molecular-weight substances may also have an unstable interface with the zinc phthalocyanine dye (A-1), leading to foreign matter formation. Conversely, when the iodine value of the photosensitive coloring resin composition exceeds 15 g / 100 g, it indicates an excessively high proportion of aliphatic segments, exacerbating the compatibility issues with the zinc phthalocyanine dye (A-1) and potentially causing excessively large foreign matter sizes after multi-stage thermal processing.

[0034] Specifically, the required iodine value of the photosensitive coloring resin composition can be achieved by controlling, but not limited to, the composition and quantity of unsaturated groups in the photosensitive coloring resin composition, while also taking into account the synergistic effect of the reactivity of the unsaturated groups and the steric hindrance caused by the molecular structure.

[0035] <Colorant (A)>

[0036] The colorant (A) comprises zinc phthalocyanine dye (A-1). In some embodiments of the invention, the colorant (A) may further comprise other colorants (A-2) besides the zinc phthalocyanine dye (A-1).

[0037] [Zinc Phthalocyanine Dye (A-1)]

[0038] In this invention, when the colorant (A) includes the zinc phthalocyanine dye (A-1), the size of foreign matter after the multi-stage thermal process of the pixel layer formed by the photosensitive coloring resin composition is small.

[0039] There is no particular limitation on the type of zinc phthalocyanine dye (A-1). In some embodiments of the present invention, preferably, the zinc phthalocyanine dye (A-1) is a compound as shown in formula (I).

[0040] (I)

[0041] In the above formula (I), A 1 To A 16 Each independently represents a hydrogen atom, a halogen atom, or a group as shown in formula (II), and A 1 To the A 16 At least one of them represents the group shown in formula (II).

[0042] (II)

[0043] In formula (II), X represents a divalent linking group, and A 17 Indicates substituted or unsubstituted phenyl groups. Indicates the location of the bond.

[0044] The A 1 To the A 16 The halogen atoms in the composition can be listed as fluorine, chlorine, and bromine atoms. From the viewpoint that the pixel layer formed from the photosensitive coloring resin composition has small-sized post-thermal foreign matter, the halogen atom is preferably a fluorine atom. In some embodiments of the invention, preferably, the A... 1 To the A 16 More than 6 of them are fluorine atoms; more preferably, the A 1 To the A 16 More than 7 of them are fluorine atoms; more preferably, the A 1 To the A 16 More than 8 of them are fluorine atoms, and preferably, the A 1 To the A 16 The number of fluorine atoms in it is 15 or less; more preferably, the A 1 To the A 16 The number of fluorine atoms in it is 12 or less; more preferably, the A 1 To the A 16The number of fluorine atoms in it is less than 10. By using the A... 1 To the A 16 Setting the number of fluorine atoms in the dye to above the aforementioned lower limit can further improve the stability of the zinc phthalocyanine dye (A-1) and reduce the size of foreign matter after the multi-segment thermal processing of the pixel layer. By using the A-1... 1 To the A 16 Setting the number of fluorine atoms in the dye below the aforementioned upper limit further enhances the affinity between the zinc phthalocyanine dye (A-1) and the solvent (E) in the photosensitive coloring resin composition. The aforementioned upper and lower limits can be combined arbitrarily; for example, preferably, A... 1 To the A 16 The number of fluorine atoms in it is 6 to 15; more preferably, the A 1 To the A 16 The number of fluorine atoms in it is 7 to 12; more preferably, the A 1 To the A 16 The number of fluorine atoms in it is between 8 and 10.

[0045] In formula (II), X represents a divalent linking group. The divalent linking group is not particularly limited and can include oxygen atoms, sulfur atoms, or -N(R) atoms. a1 )-base, R a1 The group represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Among these groups, from the viewpoint of stability during subsequent baking, it is preferable that X represents an oxygen atom or a sulfur atom; more preferably, X is an oxygen atom.

[0046] In the above formula (II), A 17 This indicates a substituted or unsubstituted phenyl group. The benzene ring in the phenyl group may have any substituents. There are no particular limitations on the substituents, and examples include halogen atoms, alkyl groups, alkoxy groups, and [-OR] groups. A base (R) A [representing alkyl], alkoxycarbonyl [-COOR] A base (R) A [representing alkyl], aryl, aryloxy [-OR] B base (R) B [representing aryl], aryloxycarbonyl [-COOR] B base (R) B (representing aryl). Among these groups, from the viewpoint of developing solubility or brightness, the substituent is preferably an alkoxycarbonyl.

[0047] The alkyl group contained in the substituent may be linear, branched, or cyclic. From the viewpoint of affinity with organic solvents, the alkyl group is preferably linear. The number of carbon atoms in the alkyl group is not particularly limited; generally, the alkyl group has 1 or more carbon atoms; preferably, the alkyl group has 2 or more carbon atoms; more preferably, the alkyl group has 6 or fewer carbon atoms; even more preferably, the alkyl group has 5 or fewer carbon atoms; and still more preferably, the alkyl group has 4 or fewer carbon atoms. By setting the number of carbon atoms in the alkyl group to the lower limit or above, aggregation and the generation of foreign matter can be suppressed. By setting the number of carbon atoms in the alkyl group to the upper limit or below, solvent affinity and stability over time can be improved. The upper and lower limits can be combined arbitrarily. For example, preferably, the alkyl group has 1 to 6 carbon atoms; more preferably, the alkyl group has 1 to 5 carbon atoms; still more preferably, the alkyl group has 1 to 4 carbon atoms; and particularly preferably, the alkyl group has 2 to 4 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, and hexyl. From the viewpoint of inhibiting aggregation, it is preferable that the alkyl group is methyl or ethyl; more preferably, it is ethyl.

[0048] The aryl group contained in the substituent can be an aromatic hydrocarbon cyclic group or an aromatic heterocyclic group. The number of carbon atoms in the aryl group is not particularly limited, but typically it is 4 or more; preferably, it is 6 or more; more preferably, it is 12 or less; even more preferably, it is 10 or less; and still more preferably, it is 8 or less. By setting the number of carbon atoms in the aryl group to the lower limit or above, aggregation caused by steric repulsion can be suppressed. By setting the number of carbon atoms in the aryl group to the upper limit or below, solvent affinity and stability over time can be improved. The upper and lower limits can be combined arbitrarily. For example, preferably, the number of carbon atoms in the aryl group is 4 to 12; more preferably, it is 4 to 10; still more preferably, it is 4 to 8; and particularly preferably, it is 6 to 8.

[0049] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group can be a monocyclic or condensed ring. Specific examples of the aromatic hydrocarbon ring group include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, and heptalene ring.

[0050] The aromatic heterocycle in the aromatic heterocyclic group can be a monocyclic or condensed ring. Specific examples of the aromatic heterocyclic groups include furan ring, thiophene ring, pyrrole ring, 2H-pyran ring, 4H-thiopyran ring, pyridine ring, 1,3-oxazole ring, isoxazole ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, benzofuran ring, 2-benzofuran ring, and benzothiophene ring. rings including 2-benzothiophene ring, 1H-pyrrolidine ring, indolering, isoindole ring, indolizine ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinolinering, isoquinoline ring, 4H-quinolidine ring, benzoimidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, phthalazine ring, 1,8-naphthyridine ring, and purine ring. ring), and pteridine ring.

[0051] The A of formula (II) 17In the phenyl group, the benzene ring may have any substituents. There is no particular limitation on the number of substituents. From the viewpoint of improving heat resistance by creating π-π packing of colorant molecules and suppressing the decrease in brightness due to colorant decomposition, it is preferable that the number of substituents is 1 for each benzene ring. When the benzene ring in the phenyl group of formula (II) has any substituents, the substitution positions may be ortho, meta, or para. From the viewpoint of achieving the closest packing structure, it is preferable that the substitution position is para.

[0052] In some embodiments of the present invention, in formula (I), preferably, A 1 To the A 16 Six or more atoms in A represent fluorine atoms. 1 To the A 16 When six or more of the components represent fluorine atoms, the pixel layer formed by the photosensitive coloring resin composition in the color filter can further reduce the size of foreign matter after multi-stage thermal processing.

[0053] In some embodiments of the present invention, in formula (I), A 1 To the A 16 One or more of the groups in A represent the group represented by formula (II). Preferably, from the viewpoint of solubility in organic solvents or brightness, A... 1 To the A 4 One or more of them are groups represented by formula (II), wherein A 5 To the A 8 One or more of them are groups represented by formula (II), wherein A 9 To the A 12 One or more of them are groups represented by formula (II), and A 13 To the A 16 One or more of the groups in A are the groups represented by formula (II); more preferably, A 1 To the A 4 Two or more of the groups in A are the groups represented by formula (II), and A 5 To the A 8 Two or more of the groups in A are the groups represented by formula (II), and A 9 To the A 12 Two or more of them are groups represented by formula (II), and A 13 To the A 16 Two or more of the groups are those represented by formula (II). Furthermore, from the viewpoint of efficiently stacking and suppressing brightness degradation, it is particularly preferable that the A... 2 The A mentioned 3 The A mentioned 6The A mentioned 7 The A mentioned 10 The A mentioned 11 The A mentioned 14 and the A mentioned above 15 The group represented by formula (II), and A 1 The A mentioned 4 The A mentioned 5 The A mentioned 8 The A mentioned 9 The A mentioned 12 The A mentioned 13 and the A mentioned above 16 It is a halogen atom.

[0054] In some embodiments of the present invention, in formula (II), preferably, A 17 This represents 4-alkoxycarbonylphenyl. When the A... 17 When 4-alkoxycarbonylphenyl is used, the pixel layer formed by the photosensitive coloring resin composition in the color filter can further reduce the size of foreign matter after multi-stage thermal processing.

[0055] Specific examples of the zinc phthalocyanine dye (A-1) may include, but are not limited to, at least one of the compounds shown in formula (1-1) to formula (1-13).

[0056] (1-1)

[0057] (1-2)

[0058] (1-3)

[0059] (1-4)

[0060] (1-5)

[0061] (1-6)

[0062] (1-7)

[0063] (1-8)

[0064] (1-9)

[0065] (1-10)

[0066] (1-11)

[0067] (1-12)

[0068] (1-13)

[0069] The zinc phthalocyanine dye (A-1) can be used alone or in combination.

[0070] The zinc phthalocyanine dye (A-1) can be prepared using existing methods, such as, but not limited to, the method described in Japanese Patent Application Publication No. 05-345861.

[0071] 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 zinc phthalocyanine dye (A-1) ranges from 5 wt% to 80 wt%; preferably, the content of the zinc phthalocyanine dye (A-1) ranges from 10 wt% to 70 wt%; more preferably, the content of the zinc phthalocyanine dye (A-1) ranges from 15 wt% to 50 wt%.

[0072] [Other colorants (A-2)]

[0073] The other colorant (A-2) may be an inorganic pigment, an organic pigment, a dye, or a combination thereof.

[0074] 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), aluminum (Al), 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.

[0075] 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.

[0076] The dyes include, but are not limited to, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, or combinations thereof.

[0077] The azo dyes include, but are not limited to, Acid Yellow 11, Acid Orange 7, Acid Red 37, Acid Red 180, Acid Blue 29, Direct Red 28, Direct Red 83, Direct Yellow 12, Direct Orange 26, Direct Green 28, Direct Green 59, Reactive Yellow 2, Reactive Red 17, Reactive Red 120, Reactive Black 5, Disperse Orange 5, Disperse Red 58, Disperse Blue 165, Basic Blue 41, Basic Red 18, Mordant Red 7, Mordant Yellow 5, Mordant Black 7, or combinations thereof.

[0078] 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.

[0079] The phthalocyanine dyes include, but are not limited to, Basic Blue 5, Direct Blue 86, or combinations thereof.

[0080] The quinone imine dyes include, but are not limited to, Basic Blue 3, Basic Blue 9, or combinations thereof.

[0081] The quinoline dyes include, but are not limited to, CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, or combinations thereof.

[0082] The nitro dyes include, but are not limited to, Acid Yellow 1, Acid Orange 3, Disperse Yellow 42, or combinations thereof.

[0083] The other colorants (A-2) can be used alone or in combination.

[0084] 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.

[0085] 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 other colorant (A-2) may range from 5 wt% to 40 wt%; preferably, the content of the other colorant (A-2) ranges from 5 wt% to 35 wt%; more preferably, the content of the other colorant (A-2) ranges from 5 wt% to 30 wt%.

[0086] 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 uniform and fine dispersion, it is preferable that the dispersant is a polymeric dispersant.

[0087] The polymeric dispersants may include (co)polymers of unsaturated carboxylic acid esters such as polyacrylates; (partial)ammonium salts, (partial)ammonium salts, or (partial) alkylammonium 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.

[0088] 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 ammonia valence.

[0089] Specific examples of polymeric dispersants containing nitrogen atoms in the main chain or side chain are listed below.

[0090] Commercially available examples of (partial)ammonium salts, (partial)ammonium salts, or (partial)alkylammonium salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid include Disperbyk 2000 and Disperbyk 2001 [all manufactured by BYK-Chemie].

[0091] Commercially available polyurethane products include Disperbyk 161 [manufactured by BYK-Chemie].

[0092] Commercially available unsaturated polyamides include Disperbyk 101 and Disperbyk 130 [manufactured by BYK-Chemie].

[0093] Commercially available examples of the aforementioned polyethylene imide derivatives include Solsperse 33500 [manufactured by Lubrizol Corporation, Japan], etc.

[0094] Commercially available examples of the polyallylamine derivatives include Ajisper PB821, Ajisper PB822, Ajisper PB824, and Ajisper PB827 [manufactured by Ajinomoto Fine-Techno].

[0095] 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.

[0096] There are no particular restrictions on the amount of dispersant used; it can be adjusted appropriately according to needs.

[0097] 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 5 wt% to 80 wt%; preferably, the content of the colorant (A) ranges from 10 wt% to 70 wt%; more preferably, the content of the colorant (A) ranges from 15 wt% to 50 wt%.

[0098] <Alkali-soluble resin (B)>

[0099] 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).

[0100] [First base-soluble resin (B-1)]

[0101] The first alkali-soluble resin (B-1) is obtained by copolymerization of an ethylene unsaturated monomer (b-1-1) containing a carboxylic acid group and other copolymerizable ethylene unsaturated monomers (b-1-2).

[0102] 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-acryloyloxyethyl succinate monoester (HOMS), etc.; unsaturated dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride, etc.; 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.

[0103] 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.

[0104] 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.

[0105] 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 ethyl acrylate, or combinations thereof.

[0106] 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.

[0107] 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. The polymerization method may include solution polymerization. In addition to the required monomer, the reaction solution of the alkali-soluble resin (B) may also include solvents, initiators, etc.

[0108] 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.

[0109] 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.

[0110] The first alkali-soluble resin (B-1) can be used alone or in combination with other resins.

[0111] 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.

[0112] 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 5 wt% to 60 wt%, preferably from 10 wt% to 55 wt%, and more preferably from 15 wt% to 50 wt%.

[0113] [Second alkali-soluble resin (B-2)]

[0114] The second alkali-soluble resin (B-2) is obtained by polymerization of a mixture comprising 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. In addition, the mixture may selectively comprise a carboxylic anhydride compound (b-2-3) and / or an epoxy-containing compound (b-2-4).

[0115] 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.

[0116] (III-1)

[0117] In the above formula (III-1), R 1c R 2c R3c and 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.

[0118] 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.

[0119] 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.

[0120] The epihalohydrin may include, but is not limited to, 3-chloro-1,2-epoxypropane (epichlorohydrin), 3-bromo-1,2-epoxypropane (epibromohydrin), or combinations thereof.

[0121] 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.

[0122] 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).

[0123] (III-2)

[0124] 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.

[0125] An epoxy compound of formula (III-2) having at least two epoxy groups (b-2-1) is obtained, for example, by reacting a compound having the structure shown in formula (III-2-1) below with a halopropane in the presence of an alkali metal hydroxide.

[0126] (III-2-1)

[0127] 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.

[0128] 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, to form a 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.

[0129] (III-2-2)

[0130] 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.

[0131] 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.

[0132] 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.

[0133] In some embodiments of the present invention, based on the amount of the compound having the structure shown in formula (III-2-2) used being 1 mole, the amount of the phenol used is from 0.5 moles to 20 moles, preferably from 2 moles to 15 moles.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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).

[0139] 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.

[0140] 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.

[0141] 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.

[0142] 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.

[0143] In some embodiments of the present invention, in order to facilitate the dehydrohalogenation reaction, in addition to adding alcohols such as methanol and ethanol, aprotic polar solvents such as dimethyl sulfone and dimethyl sulfoxide may also 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%.

[0144] 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.

[0145] 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.

[0146] 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 an epoxy compound (b-2-1) having at least two epoxy groups as shown in formula (III-2). The epoxy compound (b-2-1) having at least two epoxy groups as 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.

[0147] The compound (b-2-2) having at least one carboxylic acid group and at least one vinyl unsaturated group is, for example, selected from the group consisting of (1) to (3) below: (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-methacryloyloxypropyltetrahydrophthalic acid, 2-methacryloyloxypropylphthalic acid, 2-methacryloyloxypropyltetrahydro ... (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 trimethacrylate, etc. In addition, 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, so it will not be described again here.

[0148] 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.

[0149] 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.).

[0150] 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.

[0151] 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 with a structure 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.

[0152] 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, trimethylamine, 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, the amount of the reaction catalyst used is preferably 0.01 parts by weight to 10 parts by weight; more preferably, the amount of the reaction catalyst used is 0.3 parts by weight to 5 parts by weight.

[0153] 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.

[0154] 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.

[0155] 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.

[0156] The second alkali-soluble resin (B-2) can be used alone or in combination with other resins.

[0157] 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) ranges from 5 wt% to 60 wt%; preferably, the content of the second alkali-soluble resin (B-2) ranges from 10 wt% to 55 wt%; more preferably, the content of the second alkali-soluble resin (B-2) ranges from 15 wt% to 50 wt%.

[0158] 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) can range from 5 wt% to 60 wt%; preferably, the content of the alkali-soluble resin (B) ranges from 10 wt% to 55 wt%; more preferably, the content of the alkali-soluble resin (B) ranges from 15 wt% to 50 wt%.

[0159] <Photopolymerizable Compounds (C)>

[0160] The photopolymerizable compound (C) may include unsaturated compounds having at least one vinyl unsaturated group and unsaturated compounds having at least two vinyl unsaturated groups.

[0161] Specific examples of the unsaturated compound 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. 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, methyl methacrylate 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-vinylcortyrolone, Phenoxyethyl acrylate, Phenoxyethyl methacrylate, Pentachlorophenyl acrylate, Pentachlorophenyl methacrylate, Pentabromophenyl acrylate, Pentabromophenyl methacrylate, Polyethylene glycol monoacrylate, Polyethylene glycol monomethacrylate, Polypropylene glycol monoacrylate, Polypropylene glycol 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.

[0162] 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.

[0163] 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.

[0164] In some embodiments of the present invention, more preferably, specific examples of the photopolymerizable compound (C) are dipentaerythritol hexaacrylate, dipentaerythritol tetraacrylate, or combinations thereof.

[0165] The photopolymerizable compound (C) can be used alone or in combination.

[0166] 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 50 wt%; preferably, the content of the photopolymerizable compound (C) ranges from 8 wt% to 45 wt%; more preferably, the content of the photopolymerizable compound (C) ranges from 10 wt% to 40 wt%.

[0167] <Photoinitiator (D)>

[0168] The photoinitiator (D) may be a free radical type photoinitiator.

[0169] The photoinitiator (D) may include acetophenone, biimidazole, acyl oxime, or combinations thereof.

[0170] 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.

[0171] 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.

[0172] The acyloxime compounds are selected from ethaneone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-substituted]-, 1-(oxoacetyl oxime), such as 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), such as the product CGI-242 manufactured by Ciba Specialty Chemicals. The product CGI-124 manufactured by Chemicals Co., Ltd., with 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., with the structure shown in formula (IV-3) below], or combinations thereof.

[0173] (IV-1)

[0174] (IV-2)

[0175] (IV-3)

[0176] 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.

[0177] In some embodiments of the 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].

[0178] The photoinitiator (D) can be used alone or in combination.

[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 photoinitiator (D) can range from 0.1 wt% to 12 wt%; preferably, the content of the photoinitiator (D) ranges from 0.5 wt% to 11 wt%; more preferably, the content of the photoinitiator (D) ranges from 1 wt% to 10 wt%.

[0180] <Solvent (E)>

[0181] 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.

[0182] 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) comprises propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, or a combination thereof.

[0183] 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%.

[0184] <Additives (F)>

[0185] 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.

[0186] The filler may include glass, aluminum, or combinations thereof.

[0187] Examples of the polymeric compounds include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroacrylate, or combinations thereof.

[0188] 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-thiolylpropyltrimethoxysilane, or combinations thereof.

[0189] Examples of antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or combinations thereof.

[0190] Examples of ultraviolet absorbers include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxyphenyl ketone, or combinations thereof.

[0191] Examples of anti-agglomerating agents include sodium polyacrylate.

[0192] The additive (F) can be used alone or in combination.

[0193] 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.

[0194] 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%.

[0195] Preparation method of photosensitive coloring resin composition

[0196] 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) First, adding the colorant (A) to the solvent (E) to prepare a colorant dispersion, and then adding the alkali-soluble resin (B), the photopolymerizable compound (C), the photoinitiator (D), and the additive (F) as needed to the colorant dispersion and mixing them; (2) Simultaneously adding 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) and mixing them; (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.

[0197] In view of the above methods, it is preferable to prepare the photosensitive coloring resin composition by the methods described in (1) and (4) above, so as to effectively prevent the colorant (A) from agglomerating and to ensure uniform dispersion.

[0198] 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.

[0199] Color filters and their manufacturing methods

[0200] 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.

[0201] Specific examples of the substrate include: alkali-free glass, soda-lime glass, hard glass (Pyles glass), quartz glass, sodium glass used in liquid crystal display devices, or substrates with a transparent conductive film attached to the glass; or substrates for photoelectric conversion devices such as solid-state imaging devices (e.g., silicon substrates). The substrate typically first forms a black matrix that isolates each pixel layer.

[0202] 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%.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] Liquid Crystal Displays

[0208] 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.

[0209] As for the liquid crystals used above, that is, liquid crystal compounds or liquid crystal compositions, there are no particular limitations here, but any kind of liquid crystal compound and liquid crystal composition may be used.

[0210] 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.

[0211] [Synthetic Example B-1] First base soluble resin

[0212] 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 ensure uniform mixing of the reactants and to allow for polymerization for 4 hours. Afterward, the temperature was raised to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile were added. Polymerization was carried out for 1 hour to obtain the first alkali-soluble resin (B-1) of Synthetic Example B-1.

[0213] [Synthetic Example B-2] First base soluble resin

[0214] 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 paraben 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.

[0215] [Example 1] Photosensitive coloring resin composition

[0216] First, 27.5 parts by weight of the compound shown in Formula (1-1) [i.e., colorant (A-1-1)], 15 parts by weight of CI Pigment Yellow 138 [i.e., colorant (A-2-1)], 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 in a wide-mouth bottle. After pre-pulverization 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.

[0217] Next, 442.5 parts by weight of the colorant dispersion [containing 27.5 parts by weight of the colorant (A-1-1), 15 parts by weight of the colorant (A-2-1), and 400 parts by weight of the solvent (E-1)], 45 parts by weight of the first alkali-soluble resin of Synthetic Example B-1 [i.e., alkali-soluble resin (B-1)], 5 parts by weight of isobornyl acrylate [i.e., photopolymerizable compound (C-1)], and 2.5 parts by weight of... 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime) [i.e., photoinitiator (D-1)] and 5 parts by weight of vinyltriethoxysilane [i.e., additive (F-1)] 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 evenly with a shaking type stirrer to obtain the photosensitive coloring resin composition of Example 1.

[0218] [Examples 2 to 10 and Comparative Examples 1 to 2] Photosensitive coloring resin composition

[0219] 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 types and amounts of each component in the photosensitive coloring resin composition were changed. The specific compositions of Examples 2 to 10 and Comparative Examples 1 to 2 are shown in Tables 1 and 2, and the corresponding components in Tables 1 and 2 are shown in Table 3.

[0220] [Evaluation Items]

[0221] 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 are carried out in the same manner.

[0222] Iodine value quantification: The iodine value of the photosensitive coloring resin composition of Example 1 was determined according to the standard test method of JIS K 0070:1992. Specifically, the Widmanstätten reagent (a solution containing iodine monochloride and acetic acid) was mixed with the photosensitive coloring resin composition of Example 1 and reacted in the dark. After the reaction was completed, the remaining iodine monochloride was titrated with sodium thiosulfate to calculate the iodine value. The results are shown in Tables 1 and 2.

[0223] 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.

[0224] 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:

[0225] ◎: The size of foreign matter after multi-stage thermal processing is <2μm;

[0226] ○: 2μm ≤ 4μm after multi-stage thermal processing;

[0227] △: 4μm ≤ size of foreign matter after multi-stage thermal processing < 6μm;

[0228] ╳: The size of foreign matter after multi-stage thermal processing is ≥6μm.

[0229] Table 1

[0230]

[0231] Table 2

[0232]

[0233] Table 3

[0234]

[0235] Referring to Tables 1 and 2, the photosensitive coloring resin compositions of Examples 1 to 10 employ the colorant (A) including zinc phthalocyanine dye (A-1), and simultaneously control the iodine value of the photosensitive coloring resin composition within the range of 0.5 g / 100 g to 15 g / 100 g. 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.

[0236] Furthermore, the zinc phthalocyanine dye (A-1) with the structure shown in Formula (I) used in the photosensitive coloring resin compositions of Examples 1 to 6 and 8 to 10 all contain six or more fluorine atoms. Therefore, the size of the foreign matter after the multi-stage thermal processing in the test sample films formed by the photosensitive coloring resin compositions of Examples 1 to 6 and 8 to 10 is less than 4 μm, thus exhibiting a small size of foreign matter after the multi-stage thermal processing. On the other hand, the zinc phthalocyanine dye (A-1) with the structure shown in Formula (I) used in the photosensitive coloring resin compositions of Examples 1 to 6 and 8 to 10 all contain a group shown in Formula (II) containing 4-alkoxycarbonylphenyl. Therefore, the size of the foreign matter after the multi-stage thermal processing in the test sample films formed by the photosensitive coloring resin compositions of Examples 1 to 6 and 8 to 10 is less than 4 μm, thus exhibiting a small size of foreign matter after the multi-stage thermal processing.

[0237] Furthermore, the photosensitive coloring resin compositions of Examples 1, 2, 3, 6, 8 and 10 control the iodine value within the range of 0.9 g / 100 g to 5 g / 100 g. Therefore, the size of foreign matter in the test sample film formed by the photosensitive coloring resin compositions of Examples 1, 2, 3, 6, 8 and 10 after the multi-stage thermal process is less than 2 μm, thus having a smaller size of foreign matter after the multi-stage thermal process.

[0238] Referring to Table 2, the iodine values ​​of the photosensitive coloring resin compositions of Comparative Examples 1 and 2 were 0.3 g / 100 g and 15.5 g / 100 g, respectively. Since the iodine values ​​of the photosensitive coloring resin compositions were not controlled within the range of 0.5 g / 100 g to 15 g / 100 g, the size of foreign matter in the test sample films formed by the photosensitive coloring resin compositions of Comparative Examples 1 and 2 after the multi-stage thermal process was 6 μm or more, indicating a large size of foreign matter after the multi-stage thermal process.

[0239] In summary, the photosensitive coloring resin composition of the present invention, by employing the colorant (A) including zinc phthalocyanine dye (A-1) and simultaneously controlling the iodine value of the photosensitive coloring resin composition within the range of 0.5 g / 100 g to 15 g / 100 g, results in a film formed from the photosensitive coloring resin composition containing small-sized multi-stage post-thermal processing foreign matter. This allows the photosensitive coloring resin composition to be further prepared into a pixel layer, which, when applied to color filters and liquid crystal displays, meets the requirements of high-resolution displays. Therefore, the objective of the present invention is indeed achieved.

[0240] 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 iodine value of the photosensitive coloring resin composition ranges from 0.5 g / 100 g to 15 g / 100 g, and the colorant (A) includes zinc phthalocyanine dye (A-1).

2. The photosensitive coloring resin composition according to claim 1, characterized in that: The iodine value of the photosensitive coloring resin composition ranges from 0.7 g / 100 g to 10 g / 100 g.

3. The photosensitive coloring resin composition according to claim 1, characterized in that: The iodine value of the photosensitive coloring resin composition ranges from 0.9 g / 100 g to 5 g / 100 g.

4. The photosensitive coloring resin composition according to claim 1, characterized in that: The zinc phthalocyanine dye (A-1) is a compound as shown in formula (I). (I) In the above formula (I), A 1 To A 16 Each independently represents a hydrogen atom, a halogen atom, or a group as shown in formula (II), and A 1 To the A 16 At least one of them represents the group shown in formula (II), (II) In formula (II), X represents a divalent linking group, and A 17 Indicates substituted or unsubstituted phenyl groups. Indicates the location of the bond.

5. The photosensitive coloring resin composition according to claim 4, characterized in that: The A 1 To the A 16 Six or more in the character represent fluorine atoms.

6. The photosensitive coloring resin composition according to claim 4, characterized in that: The A 17 It represents 4-alkoxycarbonylphenyl.

7. The photosensitive coloring resin composition according to claim 1, characterized in that: Based on a total solid weight of 100 wt% of the photosensitive coloring resin composition, the content of the colorant (A) ranges from 5 wt% to 80 wt%, the content of the zinc phthalocyanine dye (A-1) ranges from 5 wt% to 80 wt%, the content of the alkali-soluble resin (B) ranges from 5 wt% to 60 wt%, the content of the photopolymerizable compound (C) ranges from 5 wt% to 50 wt%, and the content of the photoinitiator (D) ranges from 0.1 wt% to 12 wt%. Based on a total weight of 100 wt% of the photosensitive coloring resin composition, the solvent (E) content ranges from 55 wt% to 95 wt%.

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.

Images