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

Abstract

The invention provides a photosensitive resin composition, a color filter and a manufacturing method thereof, and a liquid crystal display device. The photosensitive resin composition includes a colorant (A) including a triphenylmethane colorant (A-1), an alkali-soluble resin (B), a compound (C) having an ethylenically unsaturated group, a photoinitiator (D), and a solvent (E), in which in an electron spin resonance spectrogram of the photosensitive resin composition, a g value corresponding to a characteristic peak with the maximum intensity is 1.8000-2.0400.

Description

Technical Field

[0001] The present invention relates to a resin composition, a color filter and a method for manufacturing the same, and a liquid crystal display device, and in particular to a photosensitive resin composition, a color filter and a method for manufacturing the same, and a liquid crystal display device. Background Art

[0002] Currently, color filters are widely used in applications such as color LCDs, color fax machines, and color cameras. As market demand for color LCDs continues to expand, color filter manufacturing techniques are becoming increasingly diverse, including dyeing, printing, electroplating, and dispersion methods, with the dispersion method being the most popular.

[0003] The dispersion method involves first dispersing a colorant in a photosensitive resin to form a photosensitive resin composition. This composition is then coated onto a glass substrate and exposed and developed to create a specific pattern. Repeating this coating, exposure, and development process three times creates the color filter's red (R), green (G), and blue (B) pixel color patterns (hereinafter referred to as "pixel layer" or "pattern"). Generally, to further enhance the contrast of a color filter, a black matrix (or light-shielding layer) is placed between the pixel color patterns.

[0004] In recent years, in order to achieve higher precision and energy saving and carbon reduction, it is becoming more and more popular to reduce the gap between the photomask and the coating during the exposure process of forming the pixel layer. 2 Exposure is performed at high illumination for a short period of time at a low exposure dose. In this case, the surface of the coating will cure quickly, but the bottom will not cure enough, resulting in poor linearity of the low-exposure pattern.

[0005] Therefore, how to improve the low-exposure pattern linearity of the pixel layer (pattern) in the color filter formed by the photosensitive resin composition is a problem that technicians in this field are eager to solve. Summary of the Invention

[0006] The present invention provides a photosensitive resin composition, a color filter, a method for manufacturing the same, and a liquid crystal display device, wherein a pixel layer (pattern) manufactured using the photosensitive resin composition has good low-exposure pattern linearity.

[0007] The present invention provides a photosensitive resin composition, comprising a colorant (A), an alkali-soluble resin (B), a compound having an ethylenically unsaturated group (C), a photoinitiator (D), and a solvent (E), wherein the colorant (A) comprises a triphenylmethane-based colorant (A-1). In an electron spin resonance spectrum of the photosensitive resin composition, a g value corresponding to a characteristic peak with the largest intensity is 1.8000 to 2.0400.

[0008] In one embodiment of the present invention, in the electron spin resonance spectrum of the photosensitive resin composition, the g value corresponding to the characteristic peak with the highest intensity is 1.8500-2.0200.

[0009] In one embodiment of the present invention, in the electron spin resonance spectrum of the photosensitive resin composition, the g value corresponding to the characteristic peak with the highest intensity is 1.9000-2.0100.

[0010] In one embodiment of the present invention, the triphenylmethane colorant (A-1) includes at least one selected from the group consisting of a triphenylmethane colorant (A-1-1) having a structure represented by formula (I-1), a triphenylmethane colorant (A-1-2) having a structure represented by formula (I-2), and a triphenylmethane colorant (A-1-3) having a structure represented by formula (I-3).

[0011]

[0012] In formula (I-1),

[0013] A represents a p-valent organic group, wherein the carbon atom directly bonded to nitrogen in the organic group does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to nitrogen, or an aromatic group having an aliphatic hydrocarbon group, wherein the carbon chain of the aliphatic hydrocarbon group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom, and the carbon chain of the aromatic group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom;

[0014] R 1 、R 2 、R 3 、R 4 , and R 5 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, wherein R 2 With R 3 Can bond with each other to form a ring structure, R 4 With R 5 Can bond to each other to form a ring structure, multiple R 1 、R 2 、R 3 、R 4 , and R 5 Each can be the same or different;

[0015] Ar 1 represents a substituted or unsubstituted divalent aromatic group, multiple Ar 1 Each can be the same or different;

[0016] p represents an integer greater than or equal to 2,

[0017]

[0018] In formula (I-2),

[0019] R 6 、R 7 、R 8 、R 9 、R 10 , and R 11 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, or a substituted or unsubstituted aryl group;

[0020] R 12 、R 13 , and R 14 Each independently represents an alkyl group having 1 to 8 carbon atoms, or a chlorine atom;

[0021] t and u each independently represent an integer from 0 to 4;

[0022] v represents an integer from 0 to 6;

[0023] Among them, t, u, and v are not all 0 at the same time.

[0024]

[0025] In formula (I-3),

[0026] R 15 、R 16 、R 17 、R 18 、R 19 , and R 20 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, or a substituted or unsubstituted aryl group;

[0027] R 21 、R 22 , and R 23 Each independently represents an alkyl group having 1 to 8 carbon atoms, or a chlorine atom;

[0028] f, g, and h each independently represent an integer of 0-4.

[0029] In one embodiment of the present invention, the triphenylmethane colorant (A-1) includes a triphenylmethane colorant having a structure represented by formula (I-1-1).

[0030]

[0031] In formula (I-1-1), A represents a p-valent organic group, wherein the carbon atom directly bonded to nitrogen in the organic group does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to nitrogen, or an aromatic group having an aliphatic hydrocarbon group, the carbon chain of the aliphatic hydrocarbon group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom, and the carbon chain of the aromatic group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom;

[0032] R 1 、R 2 、R 3 、R 4 , and R 5 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, wherein R 2 With R 3 Can bond with each other to form a ring structure, R 4 With R 5 Can bond to each other to form a ring structure, multiple R 1 、R 2 、R 3 、R 4 , and R 5 Each can be the same or different;

[0033] Ar 1 represents a substituted or unsubstituted divalent aromatic group, multiple Ar 1 Each can be the same or different;

[0034] B q- represents anion;

[0035] p represents an integer greater than 2;

[0036] r and s each independently represent an integer of 1 or greater.

[0037] In one embodiment of the present invention, the triphenylmethane-based colorant (A-1) includes heterogeneous polyacid anions containing at least one of molybdenum (Mo) and tungsten (W).

[0038] In one embodiment of the present invention, based on the total weight of the solid content of the photosensitive color resin composition as 100 weight%, the colorant (A) is 0.5 weight% to 60 weight%, the triphenylmethane colorant (A-1) is 0.5 weight% to 60 weight%, the alkali-soluble resin (B) is 1 weight% to 60 weight%, the compound having an ethylenically unsaturated group (C) is 5 weight% to 60 weight%, and the photoinitiator (D) is 0.1 weight% to 15 weight%.

[0039] The present invention provides a method for manufacturing a color filter, comprising: forming a pixel layer using the above-mentioned photosensitive resin composition.

[0040] The present invention provides a color filter, which is manufactured by the above-mentioned color filter manufacturing method.

[0041] The present invention provides a liquid crystal display device, comprising the color filter as described above.

[0042] Based on the foregoing, the present invention provides a photosensitive resin composition, wherein the colorant (A) contained in the photosensitive resin composition comprises a triphenylmethane-based colorant (A-1), and the g-value corresponding to the characteristic peak with the highest intensity in the electron spin resonance spectrum is 1.8000 to 2.0400. This enables the pixel layer (pattern) to have good low-exposure pattern linearity, and thus is suitable for color filters and liquid crystal display devices.

[0043] In order to make the above features and advantages of the present invention more clearly understood, embodiments are given below with reference to the accompanying drawings for detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 This is the electron spin resonance spectrum of Experimental Example 1. DETAILED DESCRIPTION

[0045] <Photosensitive resin composition>

[0046] This embodiment provides a photosensitive resin composition, comprising a colorant (A), an alkali-soluble resin (B), a compound having an ethylenically unsaturated group (C), a photoinitiator (D), and a solvent (E). Furthermore, the photosensitive resin composition of this embodiment may optionally include an additive (F).

[0047] In this example, the photosensitive resin composition was measured using an electron spin resonance (ESR) device. It is worth noting that electron spin resonance is typically displayed as a g-value, which is a function of the magnetic field intensity on the horizontal axis and the first-order derivative waveform of the absorption spectrum on the vertical axis. The g-value is a value inherent to each ESR signal and is determined by the frequency (ν) of the microwave applied to the sample and the intensity (H) of the resonant magnetic field. The ESR signal is identified by using the g-value.

[0048] The ESR signal can be used to observe resonance phenomena caused by spin transitions of unpaired electrons. The ESR signal indicates the presence of unpaired electrons in the sample. In other words, the detection of a peak in the measurement waveform with a g value on the horizontal axis indicates the detection of unpaired electrons.

[0049] In the electron spin resonance spectrum of the photosensitive resin composition of this embodiment, the g value corresponding to the characteristic peak with the largest intensity is 1.8000-2.0400, preferably 1.8500-2.0200, and more preferably 1.9000-2.0100.

[0050] When the colorant (A) includes a triphenylmethane-based colorant (A-1), and the g-value is controlled within the above range, the pattern produced using the photosensitive resin composition exhibits excellent low-exposure pattern linearity. Conversely, when the g-value is outside the above range, the pattern produced using the photosensitive resin composition exhibits poor low-exposure pattern linearity. While the detailed mechanism of this effect is unclear, the following factors are presumed to be responsible.

[0051] Generally speaking, when the exposure step is performed, the photoinitiator (free radical type photoinitiator) reacts to generate free radicals, which causes free radical polymerization between the resin and the like, and the exposed part is hardened. Even after development, the hardened material remains. However, in order to achieve higher precision and energy saving and carbon reduction, the gap between the photomask and the coating film is reduced, and the photoresistance is kept below 40 mJ / m2. 2 ) is exposed to high illumination for a short period of time at a low exposure dose of 100 nm. In this case, the coating surface cures rapidly, but the bottom portion is insufficiently cured, resulting in poor linearity of the low-exposure pattern. In contrast, if the g value is controlled within a specific range, free radical transfer occurs between the unpaired electrons of the triphenylmethane colorant (A-1) and the free radical photoinitiator, thereby stabilizing the free radical concentration and reducing the overall curing reaction rate. This reduces the curing speed of the coating surface and allows for sufficient curing at the bottom portion, effectively improving the problem of poor linearity of the low-exposure pattern.

[0052] The following details the various components of the photosensitive resin composition used in this embodiment:

[0053] Hereinafter, the “solid content of the photosensitive resin composition” refers to the components excluding the solvent (E); and the “total weight of the solid content of the photosensitive resin composition” refers to the total weight of the components excluding the solvent (E).

[0054] Hereinafter, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid, and (meth)acrylate refers to acrylate and / or methacrylate. Similarly, (meth)acryloyl refers to acryloyl and / or methacryloyl. (meth)acrylamide refers to acrylamide and / or methacrylamide.

[0055] Colorant (A)

[0056] The colorant (A) of this embodiment includes a triphenylmethane-based colorant (A-1). In addition, the colorant (A) may further include another colorant (A-2) in addition to the triphenylmethane-based colorant (A-1).

[0057] Triphenylmethane colorant (A-1)

[0058] In this embodiment, the triphenylmethane colorant (A-1) includes at least one selected from the group consisting of a triphenylmethane colorant (A-1-1), a triphenylmethane colorant (A-1-2), and a triphenylmethane colorant (A-1-3).

[0059] Notably, the photosensitive resin composition of this embodiment, by including the triphenylmethane colorant (A-1) and having a g-value within a specific range, enables patterns produced using the photosensitive resin composition to exhibit excellent low-exposure pattern linearity. When the photosensitive resin composition of this embodiment does not include the triphenylmethane colorant (A-1), patterns produced using the photosensitive resin composition exhibit poor low-exposure pattern linearity.

[0060] In another embodiment, when the triphenylmethane colorant (A-1) includes heterogeneous polyacid anions containing at least one of molybdenum (Mo) and tungsten (W), the low-exposure pattern linearity of the pattern produced by the photosensitive resin composition is better.

[0061] Triphenylmethane colorant (A-1-1)

[0062] The triphenylmethane colorant (A-1-1) has a structure represented by formula (I-1).

[0063]

[0064] In formula (I-1),

[0065] A represents a p-valent organic group, wherein the carbon atom directly bonded to nitrogen in the organic group does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to nitrogen, or an aromatic group having such an aliphatic hydrocarbon group, wherein the carbon chain of the aliphatic hydrocarbon group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom, and the carbon chain of the aromatic group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom;

[0066] R 1 、R 2 、R 3 、R 4 , and R 5 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, wherein R 2 With R 3Can bond with each other to form a ring structure, R 4 With R 5 Can bond to each other to form a ring structure, multiple R 1 、R 2 、R 3 、R 4 , and R 5 Each can be the same or different;

[0067] Ar 1 represents a substituted or unsubstituted divalent aromatic group, multiple Ar 1 Each can be the same or different;

[0068] p represents an integer of 2 or greater.

[0069] The p-valent organic group represented by A in formula (I-1) does not have a π bond to the carbon atom directly bonded to the nitrogen atom (N). The organic group is an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, or an aromatic group having such an aliphatic hydrocarbon group. The carbon chain of the aliphatic hydrocarbon group may contain an oxygen atom (O), a sulfur atom (S), or a nitrogen atom (N), and the carbon chain of the aromatic group may contain O, S, or N. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics of the cationic color-producing part, such as hue and transmittance, are not affected by the bonding group A or other color-producing parts, and the color can be maintained the same as that of the monomer.

[0070] In formula (I-1), the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N may be linear, branched, or cyclic, as long as the carbon atom at the terminal directly bonded to N does not have a π bond. Carbon atoms other than the terminal may have unsaturated bonds and may have substituents. The carbon chain of the substituent may contain O, S, or N. The carbon chain of the substituent may contain, for example, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, and the like. Hydrogen atoms may be substituted with halogen atoms, etc.

[0071] Furthermore, in A of formula (I-1), the aromatic group having the aliphatic hydrocarbon group may be a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, which may have a substituent or may be a heterocyclic ring containing O, S, or N.

[0072] In A of formula (I-1), A is preferably a cyclic aliphatic hydrocarbon group or aromatic group from the viewpoint of the robustness of the skeleton.

[0073] In formula (I-1), from the perspective of the robustness of the skeleton, the cyclic aliphatic hydrocarbon group as A is preferably a bridged alicyclic hydrocarbon group. The so-called bridged alicyclic hydrocarbon group refers to a polycyclic aliphatic hydrocarbon group having a cross-linked structure or a polycyclic structure within the aliphatic ring. Examples of the bridged alicyclic hydrocarbon group include norbornane, bicyclo[2.2.2]octane, and adamantane. The bridged alicyclic hydrocarbon group is preferably norbornane. In addition, examples of the aromatic group include groups containing a benzene ring or a naphthalene ring, and preferably a group containing a benzene ring. For example, when A is a divalent organic group, examples include linear, branched, or cyclic alkylene groups having 1 to 20 carbon atoms, or aromatic groups in which an alkylene group having 1 to 20 carbon atoms, such as xylylene, is substituted with two.

[0074] In formula (I-1), the valence p represents the number of color-developing cationic sites constituting the cation, and p represents an integer of 2 or greater. In the colorant, from the viewpoint of heat resistance, the valence p of the cation is preferably 2 or greater, more preferably 3 or greater. The upper limit of p is not particularly limited, but from the viewpoint of ease of production, p is preferably 4 or less, more preferably 3 or less.

[0075] In formula (I-1), R 1 、R 2 、R 3 、R 4 , and R 5 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

[0076] In formula (I-1), R 1 、R 2 、R 3 、R 4 , and R 5 The alkyl group in is not particularly limited, and examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, preferably linear or branched alkyl groups having 1 to 8 carbon atoms, and more preferably linear or branched alkyl groups having 1 to 5 carbon atoms. 1 、R 2 、R 3 、R 4 , and R 5 The alkyl group in is particularly preferably an ethyl group or a methyl group. The substituent group that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, and the like. Examples of the substituted alkyl group include an aralkyl group such as a benzyl group.

[0077] In formula (I-1), R 1 、R 2 、R 3 、R 4 , and R 5The aryl group in is not particularly limited, and examples thereof include phenyl and naphthyl. The substituent that the aryl group may have is not particularly limited, and examples thereof include alkyl and halogen atoms.

[0078] The so-called "R 2 With R 3 Can bond with each other to form a ring structure, R 4 With R 5 can bond to each other to form a ring structure" means that "R 2 With R 3 They can be bonded to each other through nitrogen atoms to form a ring structure, R 4 With R 5 The ring structure is not particularly limited and may be bonded to each other via a nitrogen atom to form a ring structure, and examples thereof include a pyrrolidine ring, a piperidine ring, or a morpholine ring.

[0079] In formula (I-1), from the viewpoint of chemical stability, R 1 、R 2 、R 3 、R 4 , and R 5 Preferably, each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or R 2 With R 3 bonded to each other to form a ring structure, R 4 With R 5 They are bonded to each other to form a ring structure, wherein the ring structure may be a pyrrolidine ring, a piperidine ring, or a morpholine ring.

[0080] In formula (I-1), R 1 、R 2 、R 3 、R 4 , and R 5 The above structure can be formed independently, that is, multiple R 1 、R 2 、R 3 、R 4 , and R 5 Each can be the same or different. Among them, from the perspective of color purity, R 1 A hydrogen atom is preferred. From the perspective of ease of production and raw material supply, R 2 、R 3 、R 4 , and R 5 All the same.

[0081] In formula (I-1), Ar 1 There is no particular limitation on the substituted or unsubstituted divalent aromatic group in the group. 1 Each may be the same or different. 1The aromatic group in can be the same as those exemplified for the aromatic group of A.

[0082] In formula (I-1), Ar 1 Preferred are substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms, and more preferred are substituted or unsubstituted aromatic groups containing condensed polycyclic carbocyclic rings having 10 to 14 carbon atoms. Among these, phenylene and naphthylene are more preferred from the viewpoint of simple structure and low raw material cost.

[0083] In formula (I-1), there are multiple R 1 、R 2 、R 3 、R 4 , and R 5 and Ar 1 Can be the same or different. 1 、R 2 、R 3 、R 4 , and R 5 and Ar 1 The combination can be adjusted to the desired color.

[0084] The structure shown in formula (I-1) is a cation with a valence of 2 or more, which can be combined with an anion with a valence of 2 or more. q- .

[0085] It is worth noting that since the compound represented by formula (I-1) contains anions and cations with a valence of 2 or more, the structure (cation) represented by formula (I-1) and B q- (anions) can form aggregates. Among them, anions and cations are not simply ionically bonded on a molecule-to-molecule basis, but rather multiple molecules are assembled through ion bonding to form a molecular assembly. Therefore, the molecular weight of the appearance is higher than that of the existing lake pigment. Generally speaking, it is speculated that the structure (cation) shown in formula (I-1) and B q- The aggregates formed by (anions) have a stronger cohesive force in the solid state, which reduces thermal motion and inhibits the dissociation of ion pairs or the decomposition of cationic parts, making it more difficult to fade than existing lake pigments.

[0086] In the structure shown in formula (I-1), a cation having a valence of 2 or more is combined with B q- On the premise that the anion is present, the molecular assembly can be represented by a structure shown in the following formula (I-1-1), for example.

[0087]

[0088] In formula (I-1-1), A, Ar 1 、R 1 、R 2 、R 3 、R 4 、R 5 , and p are the same as those in formula (I-1) and are not further described here. q- represents an anion, and r and s represent integers of 1 or greater.

[0089] In formula (I-1-1), r represents the number of cations, and s represents the number of anions in the molecular assembly. r and s represent integers of 1 or greater. When r represents 2 or greater, multiple cations in the molecular assembly may be used singly or in combination of two or more. Furthermore, when s represents 2 or greater, multiple anions in the molecular assembly may be used singly or in combination of two or more.

[0090] When the triphenylmethane colorant (A-1) of the photosensitive resin composition of this embodiment includes the structure represented by formula (I-1-1), the low-exposure pattern linearity of the pattern produced by the photosensitive resin composition is better.

[0091] In addition, in formula (I-1-1), B q- (anion) is not particularly limited and can be an organic anion or an inorganic anion. Here, the so-called "organic anion" means an anion containing at least one carbon atom. Also, the so-called "inorganic anion" means an anion not containing a carbon atom. In this embodiment, from the perspective of the brightness of the pixel, B q- Inorganic anions are preferred.

[0092] B q- In the case of an organic anion, its structure is not particularly limited, and examples thereof include those described in International Publication No. 2012 / 144520.

[0093] From the perspective of colorant stability, B q- Preferably, the organic anion has two or more monovalent anionic substituents in one molecule. Specific examples of anionic substituents include -SO2N - SO2CH3, -SO2N - COCH3, -SO2N - SO2CF3, -SO2N - COCF3, -CF2SO2N - SO2CH3, -CF2SO2N - COCH3, -CF2SO2N - SO2CF3, -CF2SO2N - Imido acid groups (sulfonate anions) such as COCF3, -SO3- , -CF2SO3 - 、-PO3 2- 、-COO - ,-CF2PO3 2- , and -CF2COO - From the viewpoint of high acidity to stabilize cations and maintain color development, the anionic substituent is preferably an imidic acid group, -SO3 - , -CF2SO3 - , more preferably -SO3 - (Sulfonate group) When a plurality of anionic substituents are substituted, they may be the same substituent or different substituents may be used.

[0094] On the other hand, in B q- In the case of inorganic anions, there are no particular restrictions on their structure, and examples thereof include anions of divalent or higher oxyacids (phosphate ions, sulfate ions, chromate ions, tungstate ions (WO4 2- ), molybdate ions (MoO4 2- ) etc.), multiple acid ions formed by condensation of multiple oxygen-containing acids, halogen anions, or mixtures thereof.

[0095] The polyacid anions include heterogeneous polyacid ions (M y O z ) q- or heteropolyacid ions (XM y O z ) q- In the above ion formula, M represents a polyatom, X represents a heteroatom, y represents the composition ratio of the polyatom, and z represents the composition ratio of the oxygen atom. Examples of the polyatom M include molybdenum (Mo), tungsten (W), vanadium (V), titanium (Ti), or niobium (Nb). Examples of the heteroatom X include silicon (Si), phosphorus (P), arsenic (As), sulfur (S), iron (Fe), and cobalt (Co). In addition, heterogeneous polyacid ions and heteropolyacid ions may also contain Na + or H + etc.

[0096] From the perspective of pixel brightness, B q- It is preferably a heterogeneous multiple acid anion containing at least one of molybdenum (Mo) and tungsten (W), and more preferably a heterogeneous multiple acid anion containing at least q-valent tungsten. q- When the heterogeneous polyacid anion contains at least one of molybdenum (Mo) and tungsten (W), the low-exposure pattern linearity of the pattern produced by the photosensitive resin composition is further improved.

[0097] Examples of the polyacid anion containing at least one of molybdenum (Mo) and tungsten (W) include tungstate ions [W 10 O 32 ] 4- 、Molybdate ion [Mo6O 19 ] 2- , phosphotungstate ion [PW 12 O 40 ] 3- , silicotungstate ion [SiW 12 O 40 ] 4- 、Phosphombohedral ion [PMo 12 O 40 ] 3- 、phosphotungstomolybdate ion [PW 12-a Mo a O 40 ] 3- 、H3[PW 2-b Mo b O7] 4- wait.

[0098] In the polyacid anion containing at least one of molybdenum (Mo) and tungsten (W), the molar ratio of tungsten to molybdenum is not particularly limited. From the perspective of pixel brightness, the molar ratio of tungsten to molybdenum is preferably 100:0 to 90:10.

[0099] In one embodiment, B q- represents the above-mentioned imide acid group (sulfonate anion), halogen anion, or the above-mentioned multiple acid ion.

[0100] In another embodiment, B q- Preferably, chloride ion, [PW 12 O 40 ] 3- 、[PW 11.76 Mo 0.24 O 40 ] 3- , or a combination thereof.

[0101] The method for producing the structure represented by formula (I-1) and the compound represented by formula (I-1-1) is not particularly limited, and they can be produced, for example, by referring to the specification of International Publication No. 2012 / 144520.

[0102] Specific examples of the compound represented by formula (I-1-1) include at least one of compounds (1) to (21). Each of compounds (1) to (21) contains a cation and a heterogeneous polyacid anion.

[0103] Specific examples of the compound represented by formula (I-1-1) preferably include at least one of compound (2), compound (21), and compound (22).

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112] Triphenylmethane colorant (A-1-2)

[0113] The triphenylmethane colorant (A-1-2) has a structure represented by formula (I-2).

[0114]

[0115] In formula (I-2),

[0116] R 6 、R 7 、R 8 、R 9 、R 10 , and R 11 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, or a substituted or unsubstituted aryl group;

[0117] R 12 、R 13 , and R 14 Each independently represents an alkyl group having 1 to 8 carbon atoms, or a chlorine atom;

[0118] t and u each independently represent an integer from 0 to 4;

[0119] v represents an integer from 0 to 6;

[0120] Among them, t, u, and v are not 0 at the same time.

[0121] In formula (I-2), R 6 、R 7 、R 8、R 9 、R 10 , and R 11 The alkyl group having 1 to 8 carbon atoms in the R is not particularly limited, and specific examples include straight-chain saturated hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl; isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, methylpentyl, ethylbutyl, methylhexyl, ethylpentyl, propylbutyl, (methylethyl)butyl, (methylethyl)(methyl)propyl, methylheptyl, ethylhexyl, propylpentyl, (methylethyl)pentyl, butylbutyl, dimethylpropyl, dimethylbutyl, (ethyl)(methyl)propyl, dimethylpentyl, (ethyl)(methyl)butyl, dimethylhexyl, (ethyl)(methyl)pentyl, (propyl)(methyl)butyl, (methylethyl)(methyl)butyl, and diethylbutyl. R 6 、R 7 、R 8 、R 9 、R 10 , and R 11 Preferred is an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.

[0122] In formula (I-2), R 6 、R 7 、R 8 、R 9 、R 10 , and R 11 Specific examples of the cycloalkyl group having 3 to 8 carbon atoms in R include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. 6 、R 7 、R 8 、R 9 、R 10 , and R 11 Preferred is a cycloalkyl group having 4 to 6 carbon atoms, and more preferred is a cyclohexyl group.

[0123] In formula (I-2), R 6 、R 7 、R 8 、R 9 、R 10 , and R 11 The aryl group in R includes aryl groups having 6 to 14 carbon atoms, and preferably aryl groups having 6 to 10 carbon atoms. 6 、R 7 、R 8 、R 9 、R 10 , and R 11The aryl group in the aromatic hydrocarbon ring group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring. Specific examples of the aromatic hydrocarbon ring group include a benzene ring having one free valence, a naphthalene ring, a cyclopentadiene ring, an indenering ring, an azulene ring, and a heptalene ring. The aromatic heterocyclic ring may be a monocyclic ring or a fused ring. Specific examples of the aromatic heterocyclic ring in the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1,3-oxazole ring, an isoxazole ring, a 1,3-thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazane ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 1,3,5-triazine ring, a benzofuran ring, a 2-benzofuran ring, a benzothiophene ring, and the like. ring), 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indolizine ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring, benzimidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, phthalazine ring, 1,8-naphthyridine ring, purine ring, pteridine ring, etc. In formula (I-2), R6 、R 7 、R 8 、R 9 、R 10 , and R 11 Preferred is phenyl.

[0124] In formula (I-2), R 6 、R 7 、R 8 、R 9 、R 10 , and R 11 Substituents that may be present in the alkyl group having 1 to 8 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms, and the aryl group include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a trifluoromethyl group, or a cyano group. Furthermore, the cycloalkyl group and the aryl group may be substituted with an alkyl group having 1 to 6 carbon atoms. The position and number of substituents are not particularly limited. When there are two or more substituents, the substituents may be the same or different.

[0125] In formula (I-2), R 12 、R 13 , and R 14 Each independently represents an alkyl group having 1 to 8 carbon atoms or a chlorine atom, preferably an alkyl group having 1 to 4 carbon atoms or a chlorine atom, more preferably an alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group or an ethyl group.

[0126] In formula (I-2), t and u each independently represent an integer of 0 to 4, preferably each independently represent an integer of 0 to 2; v represents an integer of 0 to 6, preferably represents 0 or 1; wherein t, u, and v are not all 0. Preferably, the combination of t, u, and v includes the combination of t = 1, u = 0, v = 0, the combination of t = 0, u = 0, v = 1, the combination of t = 2, u = 0, v = 0, the combination of t = 1, u = 1, v = 0, and the combination of t = 1, u = 1, v = 1; more preferably, the combination of t = 1, u = 0, v = 0, the combination of t = 0, u = 0, v = 1, and the combination of t = 1, u = 1, v = 0.

[0127] The structure represented by formula (I-2) is a cationic chromophoric group of a triarylmethane, and examples thereof include the chromophoric groups represented by a3 and a6 in compound group a and the chromophoric group represented by b3 in compound group b. Among them, the cationic chromophoric group of a triarylmethane is preferably a3.

[0128] [Compound Group a]

[0129]

[0130] [Compound Group b]

[0131]

[0132] In addition, the structure shown in formula (I-2) is a cation, which can be combined with anions with a valence of 2 or more. q- , where B q- B described in the above triphenylmethane colorant (A-1-1) q- The same, no further description is given here.

[0133] Triphenylmethane colorant (A-1-3)

[0134] The triphenylmethane colorant (A-1-3) has a structure represented by formula (I-3).

[0135]

[0136] In formula (I-3),

[0137] R 15 、R 16 、R 17 、R 18 、R 19 , and R 20 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, or a substituted or unsubstituted aryl group;

[0138] R 21 、R 22 , and R 23 Each independently represents an alkyl group having 1 to 8 carbon atoms, or a chlorine atom;

[0139] f, g, and h each independently represent an integer of 0-4.

[0140] In formula (I-3), R 15 、R 16 、R 17 、R 18 、R 19 , and R 20 Specific examples of the substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and its substituents and R in formula (I-2) 6 、R 7 、R 8 、R 9 、R 10 , and R 11 Specific examples of the substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and its substituents are the same as those in , and are not further described here.

[0141] In formula (I-3), R 15 、R 16 、R 17 、R18 、R 19 , and R 20 Specific examples of the substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms and its substituents and R in formula (I-2) 6 、R 7 、R 8 、R 9 、R 10 , and R 11 Specific examples of the substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms and its substituents are the same as those in , and are not further described here.

[0142] In formula (I-3), R 15 、R 16 、R 17 、R 18 、R 19 , and R 20 Specific examples of substituted or unsubstituted aryl groups and their substituents and R in formula (I-2) 6 、R 7 、R 8 、R 9 、R 10 , and R 11 The specific examples of the substituted or unsubstituted aryl group and its substituents are the same as those in , and are not further described here.

[0143] In formula (I-3), R 21 、R 22 , and R 23 Specific examples of the alkyl group having 1 to 8 carbon atoms are the same as those of R in formula (I-2). 6 、R 7 、R 8 、R 9 、R 10 , and R 11 Specific examples of the alkyl group having 1 to 8 carbon atoms are the same as those in , and are not described in detail here.

[0144] In formula (I-3), f, g, and h each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1. The combination of f, g, and h is preferably a combination of f = 0, g = 0, h = 0, a combination of f = 1, g = 0, h = 0, a combination of f = 2, g = 0, h = 0, a combination of f = 1, g = 1, h = 0, and a combination of f = 1, g = 1, h = 1; more preferably, f = 1, g = 0, h = 0, and even more preferably, a combination of f = 1, g = 1, h = 0.

[0145] The structure represented by formula (I-3) is a cationic chromophoric group of a triarylmethane, and examples thereof include the chromophoric groups a1, a2, a4, and a5 of compound group a and b1, b2, b4, b6, and b7 of compound group b. Preferred cationic chromophoric groups of the triarylmethane are a5 and b7.

[0146] In addition, the structure (cation) represented by formula (I-3) can be combined with anions having a valence of 2 or more. q- , where B q- B described in the above triphenylmethane colorant (A-1-1) q- The same, no further description is given here.

[0147] In this embodiment, based on 100 wt % of the total solid content of the photosensitive resin composition, the triphenylmethane colorant (A-1) is present in an amount of 0.5 wt % to 60 wt %, preferably 1 wt % to 55 wt %, and more preferably 5 wt % to 50 wt %.

[0148] Other colorants (A-2)

[0149] In this embodiment, the colorant (A) may further include other colorants (A-2). Other colorants (A-2) may be inorganic pigments, organic pigments, dyes, or combinations thereof.

[0150] Inorganic pigments may be metal compounds such as metal oxides and metal zirconium salts. 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 zirconium salts, or combinations thereof.

[0151] Specific examples of organic pigments 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, 167, 168, 175; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI Pigment Red 1, 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, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 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 a combination thereof.

[0152] The dyes include, but are not limited to, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, or combinations thereof.

[0153] Azo dyes include, but are not limited to, CI 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.

[0154] Anthraquinone dyes include, but are not limited to, CI Bader Blue 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.

[0155] Phthalocyanine dyes include, but are not limited to, CI Basic Blue 5, Direct Blue 86, or a combination thereof.

[0156] The quinoneimine dye includes, but is not limited to, CI Basic Blue 3, CI Basic Blue 9, or a combination thereof.

[0157] Quinoline dyes include CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, or a combination thereof.

[0158] Nitro dyes include, but are not limited to, CI Acid Yellow 1, Acid Orange 3, Disperse Yellow 42, or a combination thereof.

[0159] The above-mentioned other colorants (A-2) can be used alone or in combination of two or more.

[0160] The other colorant (A-2) is preferably CI Pigment Blue 15:4, CI Pigment Blue 15:6, or a combination thereof.

[0161] The average particle size of the other colorant (A-2) may be 10 nm to 200 nm, preferably 20 nm to 150 nm, and more preferably 30 nm to 130 nm.

[0162] In this embodiment, based on 100 wt % of the total solid content of the photosensitive resin composition, the content of the other colorant (A-2) may be 0 wt % to 40 wt %, preferably 0 wt % to 35 wt %, and more preferably 0 wt % to 30 wt %.

[0163] In this embodiment, based on 100 wt % of the total solid content of the photosensitive resin composition, the colorant (A) may be present in an amount of 0.5 wt % to 60 wt %, preferably 1 wt % to 55 wt %, and more preferably 5 wt % to 50 wt %.

[0164] In the photosensitive resin composition of this embodiment, the colorant (A) is preferably used by being dispersed in a solvent by a dispersant. In this embodiment, the dispersant can be appropriately selected from existing dispersants. Examples of the dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, silicone surfactants, fluorine surfactants and other surfactants, or combinations thereof. The dispersants listed above may be non-polymer dispersants or polymer dispersants. From the perspective of being able to disperse evenly and finely, the surfactant is preferably a polymer dispersant.

[0165] Examples of the polymer dispersant include (co)polymers of unsaturated carboxylates such as polyacrylates; (partial) amine salts, (partial) ammonium salts or (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid; (co)polymers of hydroxyl-containing unsaturated carboxylates such as hydroxyl-containing polyacrylates or modified products of the above compounds; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (amides or bases thereof obtained by reacting poly(lower alkyleneimine) with polyesters containing free carboxyl groups); polyallylamine derivatives (reaction products obtained by reacting polyallylamine with one or more compounds selected from the group consisting of polyesters containing free carboxyl groups, polyamides or co-condensates of esters and amides (polyesteramides)), or combinations thereof.

[0166] From the viewpoint of being able to preferably disperse the colorant (A) and having good dispersion stability, the polymer dispersant is preferably a polymer dispersant containing a nitrogen atom in the main chain or a side chain and having an amine value.

[0167] Specific examples of the polymer dispersant containing nitrogen atoms in the main chain or the side chain are as follows.

[0168] Commercially available products of (partial) amine salts, (partial) ammonium salts, or (partial) alkylamine salts of (co)polymers of unsaturated carboxylic acids such as polyacrylic acid include Disperbyk 2000 and Disperbyk 2001 (all manufactured by BYK-Chemie).

[0169] Examples of commercially available polyurethanes include Disperbyk 161 (manufactured by BYK-Chemie).

[0170] Examples of commercially available unsaturated polyamides include Disperbyk 101 and Disperbyk 130 (manufactured by BYK-Chemie).

[0171] Examples of commercially available polyallylamine derivatives include Ajisper PB821, Ajisper PB822, Ajisper PB824, and Ajisper PB827 (manufactured by Ajinomoto Fine-Techno Co., Ltd.).

[0172] Examples of commercially available polyethyleneimine derivatives include Solsperse 33500 (manufactured by Lubrizol Japan).

[0173] 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); EFKA 4046 and 4047 (all manufactured by EFKA Chemicals Co.); Solsperse 12000, Solsperse 13250, and Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 24000SC, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 33500, Solsperse 35200, Solsperse 37500 (all manufactured by Lubrizol Corporation of Japan); Ajisper PB711, Ajisper 823, Ajisper 880 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), etc.

[0174] The amount of the dispersant used is not particularly limited and can be appropriately adjusted according to needs.

[0175] Alkali-soluble resin (B)

[0176] The alkali-soluble resin (B) of this embodiment may include a first alkali-soluble resin (B-1). In addition, the alkali-soluble resin (B) of this embodiment may further include a second alkali-soluble resin (B-2).

[0177] First alkali-soluble resin (B-1)

[0178] The first alkali-soluble resin (B-1) of this embodiment is obtained by copolymerizing a carboxylic acid group-containing ethylenically unsaturated monomer (b-1-1) with another copolymerizable ethylenically unsaturated monomer (b-1-2).

[0179] The carboxylic acid group-containing ethylenically unsaturated monomer (b-1-1) can be used alone or in combination. Examples of such carboxylic acid group-containing ethylenically unsaturated monomers include, but are not limited to, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid (MAA), crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-acryloylethoxysuccinate, or 2-methacryloyloxyethyl succinate monoester (HOMS); unsaturated dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride; and unsaturated polycarboxylic acids (anhydrides) having three or more carboxylic acid groups. Preferred carboxylic acid group-containing ethylenically unsaturated monomers include acrylic acid, methacrylic acid, 2-acryloylethoxysuccinate, 2-methacryloylethoxysuccinate, or a combination thereof. The carboxylic acid group-containing ethylenically unsaturated monomer is more preferably 2-acryloylethoxysuccinate, 2-methacryloylethoxysuccinate, or a combination thereof.

[0180] In this embodiment, based on the usage of 100 parts by weight of the carboxylic acid group-containing ethylenically unsaturated monomer (b-1-1) and other copolymerizable ethylenically unsaturated monomers (b-1-2) of the first alkali-soluble resin (B-1), the usage of the carboxylic acid group-containing ethylenically unsaturated monomer (b-1-1) is 10 to 90 parts by weight, preferably 15 to 85 parts by weight, and more preferably 20 to 80 parts by weight.

[0181] Other copolymerizable ethylenically unsaturated monomers (b-1-2) can be used alone or in combination, and other copolymerizable ethylenically 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; maleimides such as nitrogen-phenylmaleimide (PMI), nitrogen-o-hydroxyphenylmaleimide, nitrogen-m-hydroxyphenylmaleimide, nitrogen-p-hydroxyphenylmaleimide, nitrogen-o-methylphenylmaleimide, nitrogen-m-methylphenylmaleimide, nitrogen-p-methylphenylmaleimide, nitrogen-o-methoxyphenylmaleimide, nitrogen-m-methoxyphenylmaleimide, nitrogen-p-methoxyphenylmaleimide, and nitrogen-cyclohexylmaleimide; methyl acrylate (methyl acrylate, MA for short), methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-butyl acrylate, 2-butyl methacrylate, 3-butyl acrylate, 3-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 acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate (benzyl acrylate) Unsaturated carboxylic acid esters such as benzophenone, benzophenone, benzothiazolin ...Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether, etc.; nitrified vinyl compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinyl cyanide, etc.; unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, nitrogen-hydroxyethyl acrylamide, nitrogen-hydroxyethyl methacrylamide, etc.; aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chlorinated butadiene, etc.; or combinations thereof.

[0182] Other copolymerizable ethylenically unsaturated monomers (b-1-2) preferably include styrene, nitrogen-phenylmaleimide, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, dicyclopentenyloxyethyl acrylate, or a combination thereof.

[0183] In this embodiment, the amount of the carboxylic acid group-containing ethylenically unsaturated monomer (b-1-1) and the other copolymerizable ethylenically unsaturated monomer (b-1-2) based on the first alkali-soluble resin (B-1) is 100 parts by weight, and the amount of the other copolymerizable ethylenically unsaturated monomer (b-1-2) is 10 to 90 parts by weight, preferably 15 to 85 parts by weight, and more preferably 20 to 80 parts by weight.

[0184] There is no particular limitation on the preparation method of the first alkali-soluble resin (B-1), and an appropriate polymerization method can be selected according to the needs. The polymerization method can include solution polymerization. In addition to the required monomers, the reaction solution of the alkali-soluble resin (B) may also include a solvent, an initiator, etc. The solvent can be used alone or in combination, and the solvent includes but is not limited to 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 ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, etc. (poly) alkylene glycol monoalkyl ethers; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate (propylene glycol methyl ether acetate) etheracetate (PGMEA for short), propylene glycol ethyl ether acetate, etc.; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; alkyl lactates such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc.; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (ethyl Other esters include ethyl acetate, ethyl 2-hydroxy-3-methylbutyrate, ethyl 3-methoxypropionate (EEP), ethyl ethoxylate, ethyl hydroxylate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl 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, and ethyl 2-methoxybutyrate; aromatic hydrocarbons such as toluene and xylene; and amides such as nitrogen-methylpyrrolidone, nitrogen-dimethylformamide, or nitrogen-dimethylacetamide. The solvent preferably includes propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, or a combination thereof. The (poly)alkylene glycol monoalkyl ethers refer to alkylene glycol monoalkyl ethers or polyalkylene glycol monoalkyl ethers. The (poly)alkylene glycol monoalkyl ether acetates refer to alkylene glycol monoalkyl ether acetates or polyalkylene glycol monoalkyl ether acetates.

[0185] The initiator is generally a free radical polymerization initiator, for example: azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-2-methylbutyronitrile (2,2'-azobis-2-methyl butyronitrile, abbreviated as AMBN); peroxide compounds such as dibenzoyl peroxide.

[0186] The first alkali-soluble resin (B-1) can be used alone or in combination of two or more.

[0187] Furthermore, the first alkali-soluble resin (B-1) has a polystyrene-equivalent number average molecular weight of 1,000 to 35,000, preferably 3,000 to 30,000, and more preferably 5,000 to 25,000, as measured by gel permeation chromatography (GPC).

[0188] In this embodiment, based on 100 wt % of the total solid content of the photosensitive resin composition, the first alkali-soluble resin (B-1) may be present in an amount of 1 wt % to 60 wt %, preferably 2 wt % to 55 wt %, and more preferably 3 wt % to 50 wt %.

[0189] Second alkali-soluble resin (B-2)

[0190] The second alkali-soluble resin (B-2) of this embodiment is prepared 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 ethylenically unsaturated group. Furthermore, the mixture may optionally include a carboxylic anhydride compound (b-2-3) and / or an epoxy-containing compound (b-2-4).

[0191] The epoxy compound (b-2-1) having at least two epoxy groups may have a structure as shown in the following formula (III-1) or the following formula (III-2). Here, the description of "the epoxy compound (b-2-1) may have a structure as shown in the following formula (III-1) or the following formula (III-2)" also covers the case where a compound having a structure as shown in the following formula (III-1) and a compound having a structure as shown in the following formula (III-2) coexist as the epoxy compound (b-2-1). Specifically, the epoxy compound (b-2-1) having at least two epoxy groups, for example, has a structure as shown in the following formula (III-1):

[0192]

[0193] In formula (III-1),

[0194] R 1c、 R 2c、 R 3c and R 4c Each of them 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, and R 1c、 R 2c、 R 3c and R 4c Each may be the same or different.

[0195] The epoxy compound (b-2-1) having at least two epoxy groups of the aforementioned formula (III-1) may include an epoxy-containing bisphenol fluorene compound obtained by reacting a bisphenol fluorene compound with an epihalohydrin, but is not limited thereto.

[0196] 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-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl)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 a combination thereof.

[0197] The epihalohydrin may include, but is not limited to, 3-chloro-1,2-epoxypropane (epichlorohydrin), 3-bromo-1,2-epoxypropane (epibromohydrin), or a combination thereof.

[0198] The epoxy-containing bisphenol fluorene compounds obtained by the reaction of the bisphenol fluorene compounds with 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 and EG-210; (3) products manufactured by SMS Technology Co., Ltd., such as SMS-F9PhPG, SMS-F9CrG, and SMS-F914PG; or combinations thereof.

[0199] 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):

[0200]

[0201] In formula (III-2), R 5c to R 18c Each 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 R 5c to R 18c Each can be the same or different;

[0202] g represents an integer from 0 to 10.

[0203] The epoxy compound (b-2-1) having at least two epoxy groups of the aforementioned formula (III-2) is obtained, for example, by reacting a compound having the following structure of the formula (III-2-1) with a halide propylene oxide in the presence of an alkali metal hydroxide.

[0204]

[0205] In formula (III-2-1), R 5c to R 18c and g are defined as R in formula (III-2) 5c to R 18c The definition of g is the same as that of g and will not be repeated here.

[0206] Furthermore, the epoxy compound (b-2-1) having at least two epoxy groups of the aforementioned formula (III-2) is prepared by, for example, reacting a compound having the structure of the following formula (III-2-2) with a phenol in the presence of an acid catalyst to form a compound having the structure of the formula (III-2-1). Subsequently, an excess of a halide propylene oxide is added to carry out a dehydrohalogenation reaction to obtain the epoxy compound (b-2-1) having at least two epoxy groups as shown in formula (III-2).

[0207]

[0208] In formula (III-2-2), R 19c With R 20c Each 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 R 19c With R 20c Each can be the same or different;

[0209] T 1 and T 2 Each 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 T 1 and T 2 Each may be the same or different.

[0210] The aforementioned halogen atom is preferably chlorine or bromine, the aforementioned alkyl group may be, for example, methyl, ethyl or t-butyl, and the aforementioned alkoxy group may be, for example, methoxy or ethoxy.

[0211] Specific examples of the phenols 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, and cyclohexylcresol. These phenols can generally be used alone or in combination.

[0212] Based on the usage of 1 mol of the compound having the structure of formula (III-2-2), the usage of the phenol is 0.5 mol to 20 mol, preferably 2 mol to 15 mol.

[0213] Specific examples of the acid catalyst include, but are not limited to, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride, with p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid being preferred. The acid catalysts may be used alone or in combination.

[0214] In addition, although there is no particular limitation on the amount of the acid catalyst, based on 100 weight percent (wt%) of the compound having the structure of formula (III-2-2), the amount of the acid catalyst is preferably 0.1 wt% to 30 wt%.

[0215] 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. These organic solvents can be used alone or in combination.

[0216] Based on 100 wt% of the total weight of the compound having the structure of Formula (III-2-2) and the phenol, the amount of the organic solvent is 50 wt% to 300 wt%, preferably 100 wt% to 250 wt%. Furthermore, the condensation reaction is performed at a temperature of 40°C to 180°C, and for a time of 1 to 8 hours.

[0217] After the condensation reaction is complete, a neutralization treatment or water washing treatment may be performed. The neutralization treatment adjusts the pH of the post-reaction solution to a range of pH 3 to pH 7, preferably pH 5 to pH 7. The water washing treatment may be performed using a neutralizing agent. This neutralizing agent 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 water washing treatment may be performed using conventional methods, for example, by adding an aqueous solution containing the neutralizing agent to the post-reaction solution and repeatedly extracting the solution. After neutralization or water washing, the unreacted phenols and solvent are distilled off by heating under reduced pressure, and the mixture is concentrated to obtain a compound having the structure of formula (III-2-1).

[0218] Specific examples of the aforementioned halogenated epoxypropane include, but are not limited to, 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane, or combinations thereof. An alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, may be added prior to or during the dehydrohalogenation reaction. The dehydrohalogenation reaction is performed at a temperature of 20°C to 120°C for a time of 1 to 10 hours.

[0219] In this embodiment, the alkali metal hydroxide added to the dehydrohalogenation reaction may also be an aqueous solution thereof. In this embodiment, while the aqueous alkali metal hydroxide solution is continuously added to the dehydrohalogenation reaction system, water and halogenated propylene oxide can be continuously distilled off under reduced pressure or normal pressure to separate and remove the water, while the halogenated propylene oxide can be continuously refluxed into the reaction system.

[0220] Before the dehydrohalogenation reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride may be added as a catalyst, and the mixture may be reacted at 50° C. to 150° C. for 1 to 5 hours. An alkali metal hydroxide or an aqueous solution thereof may then be added and the mixture may be reacted at 20° C. to 120° C. for 1 to 10 hours to carry out the dehydrohalogenation reaction.

[0221] Based on the total equivalent of hydroxyl groups in the compound having the structure of formula (III-2-1) being 1 equivalent, the amount of the halogenated propylene oxide used can be 1 to 20 equivalents, preferably 2 to 10 equivalents. Based on the total equivalent of hydroxyl groups in the compound having the structure of formula (III-2-1) being 1 equivalent, the amount of the alkali metal hydroxide added in the dehydrohalogenation reaction can be 0.8 to 15 equivalents, preferably 0.9 to 11 equivalents.

[0222] Furthermore, 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 to carry out the reaction. When an alcohol is used, the amount of the alcohol used may be 2 to 20 wt%, preferably 4 to 15 wt%, based on 100 wt% of the total amount of the halogenated propylene oxide. When an aprotic polar solvent is used, the amount of the aprotic polar solvent used may be 5 to 100 wt%, preferably 10 to 90 wt%, based on 100 wt% of the total amount of the halogenated propylene oxide.

[0223] After the dehydrohalogenation reaction is complete, water washing may be optionally performed. Subsequently, the halogenated propylene oxide, alcohol, and aprotic polar solvent are removed by heating and reducing pressure. This heating and reducing pressure is performed, for example, at a temperature of 110°C to 250°C and a pressure of 1.3 kPa (10 mmHg) or less.

[0224] To prevent the epoxy resin from containing hydrolyzable halogens, the solution after the dehydrohalogenation reaction can be added to a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added to perform the dehydrohalogenation reaction again. In the dehydrohalogenation reaction, based on the total equivalent weight of hydroxyl groups in the compound having the structure of formula (III-2-1) being 1 equivalent, the amount of alkali metal hydroxide used is 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol. Furthermore, the operating temperature of the dehydrohalogenation reaction is in the range of 50°C to 120°C, and the operating time is in the range of 0.5 to 2 hours.

[0225] After the dehydrohalogenation reaction is completed, salts are removed by filtering and washing. Alternatively, solvents such as toluene and methyl isobutyl ketone can be distilled off by heating and reducing 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 of formula (III-2) may include, but is not limited to, products manufactured by Nippon Kayaku Co., Ltd. under the trade names NC-3000, NC-3000H, NC-3000S, and NC-3000P.

[0226] The compound (b-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is, for example, selected from the group consisting of (1) to (3): (1) acrylic acid, methacrylic acid, 2-methacryloyloxyethylbutanedioic acid acid), 2-methacryloyloxybutylsuccinic acid, 2-methacryloyloxyethyladipic acid, 2-methacryloyloxybutyladipic acid, 2-methacryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxypropylmaleic acid, 2-methacryloyloxybutylmaleic acid, 2-methacryloyloxypropylsuccinic acid, 2-methacryloyloxypropyladipic acid, 2-methacryloyloxypropyltetrahydrophthalic acid, 2-methacryloyloxypropylphthalic acid, 2-methacryloyloxybutylphthalic acid, or 2-methacryloyloxybutylhydrophthalic acid; (2) compounds 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) compounds obtained by reacting a hydroxyl-containing (meth)acrylate with a carboxylic anhydride The half-ester compound obtained by reacting the compound with the hydroxyl group-containing (meth)acrylate includes, but is not limited to, 2-hydroxyethyl acrylate ((2-hydroxyethyl) acrylate), 2-hydroxyethyl methacrylate ((2-hydroxyethyl) methacrylate), 2-hydroxypropyl acrylate ((2-hydroxypropyl) acrylate), 2-hydroxypropyl methacrylate ((2-hydroxypropyl) methacrylate), 4-hydroxybutyl acrylate ((4-hydroxybutyl) methacrylate), or pentaerythritol trimethacrylate. The carboxylic anhydride compound described herein may be the same as the carboxylic anhydride compound (b-2-3) contained in the mixture of the second alkali-soluble resin (B-2) described below, and thus will not be described in detail here.

[0227] The mixture of the second alkali-soluble resin (B-2) may further optionally contain a carboxylic anhydride compound (b-2-3) and / or an epoxy group-containing compound (b-2-4). The carboxylic anhydride compound (b-2-3) can be selected from the group consisting of the following (1) and (2): (1) dicarboxylic anhydride compounds such as butanedioic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendo-methylene tetrahydrophthalic anhydride, chlorendic anhydride, glutaric anhydride or 1,3-dioxoisobenzofuran-5-carboxylic anhydride; and (2) benzophenone tetracarboxylic anhydride. Tetracarboxylicdianhydride (BTDA for short), diphenyl tetracarboxylic dianhydride or diphenyl ether tetracarboxylic dianhydride and other tetracarboxylic anhydride compounds.

[0228] The epoxy group-containing compound (b-2-4) is, for example, selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, an unsaturated group-containing glycidyl ether compound, an epoxy group-containing unsaturated compound, or any combination thereof. The unsaturated group-containing glycidyl ether compound includes, but is not limited to, compounds with trade names such as Denacol EX-111, EX-121Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, and Denacol EX-192 (all products of Nagase Chemicals Co., Ltd.).

[0229] The second alkali-soluble resin (B-2) can be obtained by polymerizing an epoxy compound (b-2-1) having at least two epoxy groups of formula (III-1) with a compound (b-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group to form a hydroxyl-containing reaction product, and then adding a carboxylic anhydride compound (b-2-3) to react. Based on the total hydroxyl equivalent of the hydroxyl-containing reaction product being 1 equivalent, the equivalent of the anhydride group contained in the carboxylic anhydride compound (b-2-3) is preferably 0.4 equivalents to 1 equivalent, more preferably 0.75 equivalents to 1 equivalent. When multiple carboxylic anhydride compounds (b-2-3) are used, they can be added sequentially or simultaneously in the reaction. When a dicarboxylic anhydride compound and a tetracarboxylic anhydride compound are used as the carboxylic anhydride compound (b-2-3), the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is preferably 1 / 99 to 90 / 10, more preferably 5 / 95 to 80 / 20. In addition, the operating temperature range of the above reaction is, for example, 50°C to 130°C.

[0230] The second alkali-soluble resin (B-2) can be prepared by reacting an epoxy compound (b-2-1) having at least two epoxy groups of formula (III-2) with a compound (b-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group to form a hydroxyl-containing reaction product, followed by polymerization by adding a carboxylic anhydride compound (b-2-3) and / or an epoxy-containing compound (b-2-4). The total equivalent weight of the epoxy groups on the epoxy compound (b-2-1) having at least two epoxy groups of formula (III-2) is 1 equivalent, and the acid value equivalent weight of the compound (b-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is preferably 0.8 to 1.5 equivalents, more preferably 0.9 to 1.1 equivalents. Based on the total amount of hydroxyl groups in the hydroxyl-containing reaction product being 100 mol percent (mol %), the amount of the carboxylic anhydride compound (b-2-3) used is preferably 10 mol % to 100 mol %, more preferably 20 mol % to 100 mol %, and particularly preferably 30 mol % to 100 mol %.

[0231] 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 catalysts may be used alone or in combination, and include, but are not limited to, triphenylphosphine, triphenylstibine, triethylamine, triethanolamine, tetramethylammonium chloride, and benzyltriethylammonium chloride. Based on 100 parts by weight of the total amount of the epoxy compound having at least two epoxy groups (b-2-1) and the compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (b-2-2), the amount of the reaction catalyst is preferably 0.01 to 10 parts by weight, and more preferably 0.3 to 5 parts by weight.

[0232] Furthermore, to control the degree of polymerization, a polymerization inhibitor is typically added to the reaction solution. Such polymerization inhibitors may include, but are not limited to, methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol, or phenothiazine. Generally, these polymerization inhibitors may be used alone or in combination. Based on 100 parts by weight of the combined amount of the epoxy compound having at least two epoxy groups (b-2-1) and the compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (b-2-2), the amount of the polymerization inhibitor used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

[0233] When preparing the second alkali-soluble resin (B-2), a polymerization solvent may be used as necessary. Specific examples of the polymerization reaction solvent include: alcohol compounds such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, or ethylene glycol; ketone compounds such as methyl ethyl ketone or cyclohexanone; aromatic hydrocarbon compounds such as toluene or xylene; cellosolve compounds such as cellosolve or butyl cellosolve; carbitol compounds such as carbitol or butyl carbitol; propylene glycol alkyl ether compounds such as propylene glycol monomethyl ether; polypropylene glycol alkyl ether compounds such as dipropylene glycol monomethyl ether; acetate ester compounds such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, or propylene glycol methyl ether acetate; ethyl lactate; Lactate or butyl lactate, such as alkyl lactate; dialkyl glycol ethers; or ethyl 3-ethoxypropionate. These polymerization solvents can generally be used alone or in combination. The acid value of the second alkali-soluble resin (B-2) is preferably 50 mgKOH / g to 200 mgKOH / g, more preferably 60 mgKOH / g to 150 mgKOH / g.

[0234] The second alkali-soluble resin (B-2) has a polystyrene-equivalent number average molecular weight of 500 to 10,000, preferably 800 to 8,000, and more preferably 1,000 to 6,000, as measured by colloid permeation chromatography.

[0235] The second alkali-soluble resin (B-2) can be used alone or in combination of two or more.

[0236] In this embodiment, based on 100 wt % of the total solid content of the photosensitive resin composition, the second alkali-soluble resin (B-2) may be 1 wt % to 60 wt %, preferably 2 wt % to 55 wt %, and more preferably 3 wt % to 50 wt %.

[0237] In this embodiment, based on 100 wt % of the total solid content of the photosensitive resin composition, the alkali-soluble resin (B) may be 1 wt % to 60 wt %, preferably 2 wt % to 55 wt %, and more preferably 3 wt % to 50 wt %.

[0238] Compound (C) having an ethylenically unsaturated group

[0239] The compound (C) having an ethylenically unsaturated group in this embodiment may include an unsaturated compound having at least one ethylenically unsaturated group and an unsaturated compound having at least two ethylenically unsaturated groups.

[0240] Specific examples of the unsaturated compound having at least one ethylenically unsaturated group include, but are not limited to, acrylamide, acryloylmorpholine, methacryloylmorpholine, 7-amino-3,7-dimethyloctyl acrylate, 7-amino-3,7-dimethyloctyl methacrylate, isobutoxymethylacrylamide, isobutoxymethylmethacrylamide, isobornyloxyethyl acrylate, isobornyloxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate. , ethyl diglycol acrylate, ethyl diglycol methacrylate, tert-octyl acrylamide, tert-octyl methacrylamide, diacetone acrylamide, diacetone methacrylamide, dimethylamino acrylate, dimethylamino methacrylate, dodecyl acrylate, dodecyl methacrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, tetrachlorophenyl acrylate, methyl acrylate 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, acrylate 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, vinyl caprolactam, N-vinyl pyroxanone, phenoxyethyl acrylate, phenoxyethyl methacrylate, pentachlorophenyl acrylate, pentachlorophenyl methacrylate, pentabromophenyl acrylate, pentabromophenyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, bornyl acrylate, bornyl methacrylate, or a combination thereof. The unsaturated compound having at least one ethylenically unsaturated group may be used alone or in combination.

[0241] Specific examples of the unsaturated compound having at least two ethylenically unsaturated groups include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentenyl diacrylate, dicyclopentenyl dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tris(2-hydroxyethyl)isocyanate diacrylate, tris(2-hydroxyethyl)isocyanate dimethacrylate, tris(2-hydroxyethyl)isocyanate triacrylate, tris(2-hydroxyethyl)isocyanate trimethacrylate, caprolactone-modified tris(2-hydroxyethyl)isocyanate triacrylate, caprolactone-modified tris(2-hydroxyethyl)isocyanate -hydroxyethyl) isocyanate trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene oxide (hereinafter referred to as EO) modified trimethylolpropane triacrylate, EO modified trimethylolpropane trimethacrylate, propylene oxide (hereinafter referred to as PO) modified trimethylolpropane triacrylate, PO modified trimethylolpropane 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 (dipentaerythritol hexaacrylate, DPHA), dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, caprolactone-modified dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexamethacrylate, caprolactone-modified dipentaerythritol pentaacrylate, caprolactone-modified dipentaerythritol pentamethacrylate, trimethylolpropane tetraacrylate, trimethylolpropane tetramethacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol A dimethacrylate, PO-modified 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 glycerol tripropionate, EO-modified bisphenol F diacrylate, EO-modified bisphenol F dimethacrylate, phenolic polyglycidyl ether acrylate, phenolic polyglycidyl ether methacrylate, a product manufactured by Toagosei Co., Ltd. with the model number TO-1382, or a product manufactured by Nippon Kayaku Co., Ltd. with the model numbers KAYARAD DPCA-12, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, or KAYARAD DPCA-120. The unsaturated compound having at least two ethylenically unsaturated groups may be used alone or in combination.

[0242] Specific examples of the compound (C) having an ethylenically unsaturated group preferably include trimethylolpropane triacrylate, EO-modified trimethylolpropane trimethacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, PO-modified glycerol tripropionate, KAYARAD DPCA-12, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, or KAYARAD DPCA-120, or a combination thereof.

[0243] More preferably, the compound (C) having an ethylenically unsaturated group is dipentaerythritol hexaacrylate, dipentaerythritol tetraacrylate, or a combination thereof.

[0244] The above-mentioned compound (C) having an ethylenically unsaturated group can be used alone or in combination of two or more.

[0245] In this embodiment, based on 100 wt % of the total weight of the solid components of the photosensitive resin composition, the compound (C) having an ethylenically unsaturated group may be 5 wt % to 60 wt %, preferably 8 wt % to 55 wt %, and more preferably 10 wt % to 50 wt %.

[0246] Photoinitiator (D)

[0247] The photoinitiator (D) of this embodiment may be a free radical photoinitiator.

[0248] Examples of the photoinitiator (D) include acetophenone compounds, biimidazole compounds, acyl oxime compounds, and combinations thereof.

[0249] The acetophenone compound is selected from p-dimethylamino-acetophenone, α,α'-dimethoxyazoxy-acetophenone, 2,2'-dimethyl-2-phenyl-acetophenone, p-methoxy-acetophenone, 2-methyl-1-(4

[0250] -methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone, or a combination thereof.

[0251] The diimidazole compound is selected from 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(o-fluorophenyl)-4,4,5,5'-tetraphenyl-biimidazole, s(o-fluorophenyl)-4,4',5,5'-tetraphenyl-biimidazole), 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 azole), 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole, imidazole), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole), 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole, or a combination thereof.

[0252] The acyl oxime compound is selected from ethane ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), such as CGI-242 manufactured by Ciba Specialty Chemicals, whose structure is shown in the following formula (IV-1), 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyloxime), such as 1-[4-(benzoyl)phenyl]-hept ... Chemicals) company, the product with the trade name CGI-124, whose structure is shown in the following formula (IV-2)), ethane ketone, 1-[9-ethyl-6-(2-chloro-4-benzyl-thio-benzoyl)-9-hydrogen-carbazole-3-substituent]-, 1-(oxy-acetyl oxime)

[0253] -cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime), for example, manufactured by Asahi Denka Corporation, whose structure is shown in the following formula (IV-3)), or a combination thereof.

[0254]

[0255] In one embodiment, the photoinitiator (D) may further include benzophenone compounds such as thioxanthone, 2,4-diethylthioxanthanone, 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; benzoinmethylether, benzoinethylether, and benzoinisopropylether. ether); acylphosphineoxide compounds such as 2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide and bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-benzyl-phosphineoxide; quinone compounds such as anthraquinone and 1,4-naphthoquinone; halides such as phenacyl chloride, tribromomethyl-phenylsulfone, and tris(trichloromethyl)-s-triazine; and peroxides such as di-tertbutylperoxide. Among them, benzophenone compounds are preferred, and 4,4'-bis(diethylamino)benzophenone is particularly preferred.

[0256] The photoinitiator (D) preferably includes 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime) (for example, CGI-124 manufactured by Ciba Specialty Chemicals).

[0257] The above-mentioned photoinitiators (D) can be used alone or in combination of two or more.

[0258] In this embodiment, based on 100 wt % of the total solid weight of the photosensitive resin composition, the photoinitiator (D) may be present in an amount of 0.1 wt % to 15 wt %, preferably 0.5 wt % to 13 wt %, and more preferably 1 wt % to 10 wt %.

[0259] Solvent (E)

[0260] The photosensitive resin composition of this embodiment is typically prepared by first dissolving all ingredients other than the colorant (A) in a solvent (E) to form a liquid composition. The colorant (A) is then added and uniformly mixed. The solvent (E) should be selected to dissolve the alkali-soluble resin (B), the compound having an ethylenically unsaturated group (C), and the photoinitiator (D), while also being non-reactive with these ingredients and possessing suitable volatility. Furthermore, when an additive (F) is added, the solvent (E) should be selected to dissolve the additive (F), be non-reactive with these ingredients, and possess suitable volatility.

[0261] In addition, the solvent (E) can be the same as the solvent used to prepare the alkali-soluble resin (B), and will not be described in detail here. The solvents can be used alone or in combination. Preferably, the solvent (E) includes propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, or a combination thereof.

[0262] In this embodiment, based on 100 wt % of the total weight of the photosensitive resin composition, the solvent (E) may be 55 wt % to 95 wt %, preferably 60 wt % to 95 wt %, and more preferably 70 wt % to 95 wt %.

[0263] Additives (F)

[0264] In this embodiment, the photosensitive resin composition further includes additives (F), such as fillers, polymer compounds other than the alkali-soluble resin (B), adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents, and the like.

[0265] Examples of fillers include glass, aluminum, or a combination thereof.

[0266] Examples of the polymer compound include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and combinations thereof.

[0267] Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidolpropyltrimethoxysilane, 3-glycidolpropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-thiolpropyltrimethoxysilane, or a combination thereof.

[0268] Examples of the antioxidant include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, and combinations thereof.

[0269] Examples of the ultraviolet absorber include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxyphenone, or a combination thereof.

[0270] As the anti-agglomeration agent, sodium polyacrylate can be mentioned.

[0271] The above-mentioned additives (F) can be used alone or in combination.

[0272] The additive (F) is preferably 3-mercaptopropyltrimethoxysilane, 2,2-thiobis(4-methyl-6-tert-butylphenol), or a combination thereof.

[0273] In this embodiment, based on 100 wt % of the total weight of the photosensitive resin composition, the additive (F) may be 10 wt % or less, preferably 7 wt % or less, and more preferably 5 wt % or less.

[0274] <Preparation Method of Photosensitive Resin Composition>

[0275] The preparation method of the photosensitive resin composition of this embodiment is not particularly limited. Specifically, the preparation method of the photosensitive resin composition can be listed as follows: (1) First, a colorant (A) is added to a solvent (E) to prepare a colorant dispersion, and then an alkali-soluble resin (B), a compound having an ethylenically unsaturated group (C), a photoinitiator (D), and an additive (F) used as needed are added to the colorant dispersion and mixed; (2) A colorant (A), an alkali-soluble resin (B), a compound having an ethylenically unsaturated group (C), a photoinitiator (D), and an additive (F) used as needed are added to a solvent (E) at the same time and mixed; (3) First, a colorant (A) is added to a solvent (E) to prepare a colorant dispersion, and then an alkali-soluble resin (B), a compound having an ethylenically unsaturated group (C), a photoinitiator (D), and an additive (F) used as needed are added to the colorant dispersion and mixed; A method in which an alkali-soluble resin (B), a compound having an ethylenically unsaturated group (C), a photoinitiator (D), and an optional additive (F) are first added to a solvent (E) and mixed, and then a colorant (A) is added and dispersed; and (4) a method in which a colorant (A) and a portion of an alkali-soluble resin (B) are first added to a solvent (E) to prepare a colorant dispersion, and then another portion of an alkali-soluble resin (B), a compound having an ethylenically unsaturated group (C), a photoinitiator (D), and an optional additive (F) are added to the colorant dispersion and mixed.

[0276] Among these methods, the above methods (1) and (4) are preferred from the viewpoint of being able to effectively prevent the colorant from agglomerating and achieve uniform dispersion.

[0277] The components can be uniformly dispersed / mixed using a stirrer and / or a disperser for mixing and / or dispersing. Examples of dispersers include roller mills such as double-roll mills and triple-roll mills, ball mills such as ball mills and vibrating ball mills, paint conditioners, continuous disc bead mills, and continuous ring bead mills. The bead mill dispersion conditions are preferably such that the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.

[0278] <Method for Manufacturing Color Filter>

[0279] The method for manufacturing a color filter of this embodiment includes forming a pixel layer using the photosensitive resin composition described above. Specifically, the photosensitive resin composition, mixed in a solution, is applied to a substrate via a coating method such as rotary coating, cast coating, inkjet coating, or roll coating. After coating, the composition is first dried under reduced pressure to remove most of the solvent, and then pre-baked to remove the solvent, forming a pre-baked coating film. The conditions for the reduced pressure drying and pre-baking vary depending on the type and ratio of the components. Typically, the reduced pressure drying is performed at a pressure of 0 to 200 mmHg for 1 to 60 seconds, and the pre-baking is performed at a temperature of 70 to 110°C for 1 to 15 minutes. After pre-baking, the pre-baked coating film is exposed to light through a designated mask and then immersed in a developer at 23±2°C for 15 seconds to 5 minutes for development, removing unwanted portions to form a pattern (pixel layer). The light used for exposure is preferably ultraviolet light such as g-line, h-line, i-line, etc., and the ultraviolet device can be a (super) high-pressure mercury lamp or a metal halide lamp.

[0280] Specific examples of the aforementioned substrate include alkali-free glass, soda-lime glass, hard glass (Pyles glass), quartz glass, soda glass, or substrates with a transparent conductive film attached to these glass types used in liquid crystal displays; or optoelectronic device substrates (e.g., silicon substrates) used in solid-state imaging devices. These substrates typically first form a black matrix that isolates each pixel layer.

[0281] Furthermore, specific examples of the developer include an alkaline aqueous solution composed of at least one alkaline compound selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene, with a concentration generally ranging from 0.001 to 10% by weight, preferably from 0.005 to 5% by weight, and more preferably from 0.01 to 1% by weight.

[0282] When the developer composed of the aforementioned alkaline aqueous solution is used, it is generally washed with water after development, and then the pattern is air-dried with compressed air or compressed nitrogen.

[0283] After air drying, the substrate with the photocurable coating is heated using a hot plate or oven at a temperature of 100 to 280°C for 1 to 15 minutes to remove volatile components from the coating and to thermally cure any unreacted ethylenically unsaturated double bonds. This process is repeated three times using a photosensitive resin composition of each color (primarily red, green, and blue) on the desired pixels to create the three color pixel layers.

[0284] Secondly, an ITO (indium tin oxide) vapor-deposited film is formed on the pixel layer at a temperature of 220°C to 250°C under vacuum. If necessary, the ITO vapor-deposited film is etched and wired, and then coated with polyimide for liquid crystal alignment film and heat-treated to serve as a color filter for liquid crystal displays.

[0285] Furthermore, the liquid crystal alignment film used above is used to control the alignment of liquid crystal molecules. It is not particularly limited here and can be made of any inorganic or organic material. The technology for forming the liquid crystal alignment film is well known to those skilled in the art and is not the focus of the present invention, so it will not be described in detail.

[0286] <Liquid Crystal Display Device>

[0287] The liquid crystal display device of this embodiment includes a color filter substrate containing a color filter manufactured using the color filter manufacturing method described above; and a driver substrate equipped with thin-film transistors (TFTs). The liquid crystal display device of this embodiment is constructed by placing two substrates facing each other with a gap (cell gap) interposed between them. The two substrates are bonded together with a sealant around their periphery. Liquid crystal is injected into the gap defined by the sealant and the substrate surfaces, sealing the injection hole to form a liquid crystal cell. Polarizing plates are then bonded to the outer surfaces of the liquid crystal cells, i.e., the other side surfaces of each substrate forming the liquid crystal cell, to complete the liquid crystal display device.

[0288] The liquid crystal used herein, ie, the liquid crystal compound or liquid crystal composition, is not particularly limited, and any liquid crystal compound or liquid crystal composition may be used.

[0289] The present invention will be further described with reference to the following experimental examples. However, it should be understood that these experimental examples are only for illustration and should not be construed as limiting the implementation of the present invention.

[0290] Synthesis Example of Alkali-Soluble Resin (B)

[0291] Synthesis Example B-1

[0292] 1 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 nitrogen-phenylmaleimide were placed in a round-bottom flask equipped with a stirrer and a condenser. The flask was then filled with nitrogen. The flask was then slowly stirred and heated to 80°C to uniformly mix the reactants. A polymerization reaction was then carried out for 4 hours. The temperature was then raised to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile was added. After polymerization for 1 hour, the first alkali-soluble resin of Synthesis Example B-1 was obtained.

[0293] Synthesis Example B-2

[0294] 2 parts by weight of 2,2'-azobisisobutyronitrile, 300 parts by weight of dipropylene glycol methyl ether, 15 parts by weight of methacrylic acid, 15 parts by weight of 2-hydroxyethyl acrylate, and 70 parts by weight of benzyl methacrylate were placed in a round-bottom flask equipped with a stirrer and a condenser. The flask was filled with nitrogen. The mixture was then slowly stirred and heated to 80°C to uniformly mix the reactants. A polymerization reaction was then carried out for 3 hours. The temperature was then raised to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile was added. After polymerization for 1 hour, the first alkali-soluble resin of Synthesis Example B-2 was obtained.

[0295] Experimental Examples 1 to 10 and Comparative Examples 1 to 10

[0296] The following describes Experimental Examples 1 to 10 and Comparative Examples 1 and 2 of the photosensitive resin composition:

[0297] Experimental Example 1

[0298] First, 32.5 parts by weight of compound (22) (i.e., colorant (A1-1)) propylene glycol methyl ether acetate (PGMEA, manufactured by Daicel-Allnex) and 2.0 parts by weight of zirconia beads with a particle size of 2 mm were placed in a 30 ml wide-mouth bottle. After preliminary grinding using a paint shaker (PCMH-C50M, manufactured by Asada Steel) for 1 hour, the solution was transferred to another 30 ml wide-mouth bottle, 2.0 parts by weight of zirconia beads with a particle size of 0.1 mm were added, and the mixture was shaken using a paint shaker for 20 hours to obtain the colorant dispersion of Experimental Example 1.

[0299] Next, 432.5 parts by weight of the colorant dispersion (containing 32.5 parts by weight of compound (22) and 400 parts by weight of propylene glycol methyl ether acetate), 45 parts by weight of the first alkali-soluble resin of Synthesis Example B-1 (i.e., alkali-soluble resin (B-1)), 20 parts by weight of dipentaerythritol hexaacrylate (i.e., compound (C-1) having an ethylenically unsaturated group), and 2.5 parts by weight of 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-phenylacyl oxime) (i.e., photoinitiator (D-1)) were added to a mixed solvent of 600 parts by weight of propylene glycol methyl ether acetate (i.e., solvent (E-1)) and 200 parts by weight of ethyl 3-ethoxypropionate (i.e., solvent (E-2)). The mixture was stirred uniformly with a shaking stirrer to obtain the photosensitive resin composition of Experimental Example 1.

[0300] The photosensitive resin composition of Experimental Example 1 thus prepared was evaluated using the evaluation method described below. The results are shown in Table 1.

[0301] Experimental Examples 2 to 10, Comparative Example 1, and Comparative Example 2

[0302] The photosensitive resin compositions of Experimental Examples 2 to 10, Comparative Example 1, and Comparative Example 2 were prepared using the same procedures as Experimental Example 1, except that the types and amounts of components in the photosensitive resin compositions were varied. Experimental Examples 2 to 10, Comparative Example 1, and Comparative Example 2 are shown in Table 1. The corresponding components in Table 1 are shown in Table 2. The resulting photosensitive resin compositions were evaluated using the evaluation method described below. The results of Experimental Examples 2 to 10, Comparative Example 1, and Comparative Example 2 are shown in Table 1.

[0303]

[0304] Table 2

[0305]

[0306] [Evaluation method]

[0307] a. Electron Spin Resonance (ESR)

[0308] The photosensitive resin compositions of the experimental examples and comparative examples were sealed in the innermost part of a sample tube (made of quartz, manufactured by JEOL Ltd., for X-Band, 100 mm) filled with nitrogen, and then nitrogen was refilled. The sample tube was then covered with an ESR test tube cap (manufactured by JEOL Ltd.) to obtain a sample tube filled with the sample. Finally, at room temperature and pressure, an electron spin resonance device (JES FA200, manufactured by JEOL Ltd.) was used to perform ESR measurement (the measurement conditions of the electron spin resonance device are described below), and the g value corresponding to the characteristic peak with the largest intensity in the ESR signal was recorded. Taking Experimental Example 1 as an example, Figure 1 This is the electron spin resonance spectrum of Experimental Example 1. Figure 1 It can be observed that the g value corresponding to the strongest characteristic peak in the ESR signal is 2.0071.

[0309] The measurement conditions of the electron spin resonance device are as follows:

[0310] Microwave power: 15mW;

[0311] Modulated magnetic field: 0.6m T;

[0312] Response: 0.02 seconds;

[0313] Magnetic field: 351.4 mT;

[0314] Magnetic field scanning width: ±5m T;

[0315] Increase rate: 500.

[0316] b. Low exposure pattern linearity

[0317] The photosensitive resin compositions of the experimental example and the comparative example were each coated on a glass substrate having a length and width of 100 mm by spin coating. Then, the glass substrate was dried under reduced pressure for about 30 seconds at a pressure of about 100 mmHg. Next, the glass substrate was pre-baked at 80°C for 3 minutes to form a pre-baked coating film with a thickness of 2.5 μm. Afterwards, an exposure machine (manufactured by Canon, model PLA-501F) was used to expose the glass substrate at a rate of 40 mJ / m 2 The pre-baked coating was irradiated with ultraviolet light. After irradiation with ultraviolet light, the pre-baked coating was immersed in a developer at 23°C for 2 minutes. The pre-baked coating was then rinsed with pure water and post-baked at 200°C for 80 minutes. This formed a 2.0-micron-thick photosensitive resin layer with a stripe pattern (hereinafter also referred to as the "pixel layer" or "pattern") on the glass substrate.

[0318] The stripe pattern formed by the above method was observed using an optical microscope to determine the ratio (L) of patterns with good linearity, and the low-exposure pattern linearity was evaluated according to the following criteria.

[0319] ◎: L ≧ 90%;

[0320] ○: 80% ≤ L < 90%;

[0321] △: 70% ≤ L < 80%;

[0322] ×: L<70%.

[0323] <Evaluation Results>

[0324] As shown in Table 1, when the colorant (A) includes a triphenylmethane-based colorant (A-1), and the g-value corresponding to the characteristic peak with the highest intensity is between 1.8000 and 2.0400 (Experimental Examples 1 to 10), the pattern produced by the photosensitive resin composition has good low-exposure pattern linearity.

[0325] In contrast, when the colorant (A) did not include the triphenylmethane colorant (A-1) (Comparative Examples 1 and 2), the low-exposure pattern linearity of the pixel layer produced by the photosensitive resin composition was poor. Furthermore, when the g-value corresponding to the characteristic peak with the highest intensity was not within the range of 1.8000 to 2.0400 (Comparative Examples 1 and 2), the low-exposure pattern linearity of the pixel layer produced by the photosensitive resin composition was poor.

[0326] When the triphenylmethane colorant (A-1) of the photosensitive resin composition includes the structure represented by formula (I-1-1) (Examples 1 to 3, 7 to 9), the low-exposure pattern linearity of the pattern produced by the photosensitive resin composition is further improved.

[0327] When the triphenylmethane colorant (A-1) includes heterogeneous polyacid anions containing at least one of molybdenum (Mo) and tungsten (W) (Examples 1, 2, 4, 5, 7, 8, and 10), the low-exposure pattern linearity of the pattern produced by the photosensitive resin composition is improved.

[0328] In summary, the present invention provides a photosensitive resin composition, wherein the colorant (A) contained in the photosensitive resin composition includes a triphenylmethane-based colorant (A-1), and the g-value corresponding to the characteristic peak with the highest intensity in the electron spin resonance spectrum is 1.8000 to 2.0400. This enables the pixel layer (pattern) to have good low-exposure pattern linearity, and thus is suitable for color filters and liquid crystal display devices.

[0329] Although the present invention has been disclosed above by way of embodiments, they are not intended to limit the present invention. Any person skilled in the art may make slight changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the claims.

Claims

1. A photosensitive resin composition comprising: Colorant (A), including triphenylmethane-based colorant (A-1); Alkali-soluble resin (B); A compound (C) having an ethylenically unsaturated group; a photoinitiator (D); and Solvent (E), In the electron spin resonance spectrum of the photosensitive resin composition, the g value corresponding to the characteristic peak with the largest intensity is 1.8000-2.0400. 2 . The photosensitive resin composition according to claim 1 , wherein in an electron spin resonance spectrum of the photosensitive resin composition, a g value corresponding to a characteristic peak with the largest intensity is 1.8500 to 2.0200. 3 . The photosensitive resin composition according to claim 1 , wherein in an electron spin resonance spectrum of the photosensitive resin composition, a g value corresponding to a characteristic peak with the largest intensity is 1.9000 to 2.0100.

4. The photosensitive resin composition according to claim 1, wherein the triphenylmethane colorant (A-1) comprises at least one selected from the group consisting of a triphenylmethane colorant (A-1-1) having a structure represented by formula (I-1), a triphenylmethane colorant (A-1-2) having a structure represented by formula (I-2), and a triphenylmethane colorant (A-1-3) having a structure represented by formula (I-3). In formula (I-1), A represents a p-valent organic group, wherein the carbon atom directly bonded to nitrogen in the organic group does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to nitrogen, or an aromatic group having such an aliphatic hydrocarbon group, wherein the carbon chain of the aliphatic hydrocarbon group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom, and the carbon chain of the aromatic group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom; R 1 、R 2 、R 3 、R 4 , and R 5 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, wherein R 2 With R 3 Can bond with each other to form a ring structure, R 4 With R 5 Can bond to each other to form a ring structure, multiple R 1 、R 2 、R 3 、R 4 , and R 5 Each can be the same or different; Ar 1 represents a substituted or unsubstituted divalent aromatic group, multiple Ar 1 Each can be the same or different; p represents an integer greater than or equal to 2, In formula (I-2), R 6 、R 7 、R 8 、R 9 、R 10 , and R 11 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, or a substituted or unsubstituted aryl group; R 12 、R 13 , and R 14 Each independently represents an alkyl group having 1 to 8 carbon atoms, or a chlorine atom; t and u each independently represent an integer from 0 to 4; v represents an integer from 0 to 6; in, t, u, and v are not all 0 at the same time, In formula (I-3), R 15 、R 16 、R 17 、R 18 、R 19 , and R 20 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms, or a substituted or unsubstituted aryl group; R 21 、R 22 , and R 23 Each independently represents an alkyl group having 1 to 8 carbon atoms, or a chlorine atom; f, g, and h each independently represent an integer of 0-4.

5. The photosensitive resin composition according to claim 4, wherein the triphenylmethane colorant (A-1) comprises a triphenylmethane colorant having a structure represented by formula (I-1-1), In formula (I-1-1), A represents a p-valent organic group, wherein the carbon atom directly bonded to nitrogen in the organic group does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to nitrogen, or an aromatic group having such an aliphatic hydrocarbon group, the carbon chain of the aliphatic hydrocarbon group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom, and the carbon chain of the aromatic group may contain at least one of an oxygen atom, a sulfur atom, and a nitrogen atom; R 1 、R 2 、R 3 、R 4 , and R 5 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, wherein R 2 With R 3 Can bond with each other to form a ring structure, R 4 With R 5 Can bond to each other to form a ring structure, multiple R 1 、R 2 、R 3 、R 4 , and R 5 Each can be the same or different; Ar 1 represents a substituted or unsubstituted divalent aromatic group, multiple Ar 1 Each can be the same or different; B q- represents anion; p represents an integer greater than 2; r and s each independently represent an integer of 1 or greater. The photosensitive resin composition according to claim 1 , wherein the triphenylmethane-based colorant (A-1) comprises a heterogeneous polyacid anion containing at least one of molybdenum (Mo) and tungsten (W).

7. The photosensitive resin composition according to claim 1, wherein the colorant (A) is present in an amount of 0.5 to 60% by weight, the triphenylmethane colorant (A-1) is present in an amount of 0.5 to 60% by weight, the alkali-soluble resin (B) is present in an amount of 1 to 60% by weight, the compound having an ethylenically unsaturated group (C) is present in an amount of 5 to 60% by weight, and the photoinitiator (D) is present in an amount of 0.1 to 15% by weight, based on 100% by weight of the total solid content of the photosensitive colored resin composition.

8. A method for manufacturing a color filter, comprising: A pixel layer is formed using the photosensitive resin composition according to any one of claims 1 to 7.

9. A color filter manufactured by the color filter manufacturing method according to claim 8.

10. A liquid crystal display device comprising the color filter according to claim 9.

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