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

Abstract

The invention provides a photosensitive colored resin composition, a color filter and a manufacturing method thereof, and a liquid crystal display device. The pixel layer manufactured by using the photosensitive colored resin composition has good high-fineness pattern linearity. The photosensitive colored resin composition comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D) and a solvent (E), and in an electron spin resonance spectrogram of the photosensitive colored resin composition, the g value corresponding to a characteristic peak with the maximum intensity is 1.990-2.020.

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 colored resin composition, a color filter and a method for manufacturing the same, and a liquid crystal display device. Background Art

[0002] At present, color filters are widely used in color liquid crystal displays, color fax machines, color cameras and other application fields. As the market demand for color liquid crystal displays continues to expand, the production technology of color filters has also tended to be diversified, such as dyeing, printing, electroplating and dispersion, among which the dispersion method is the mainstream.

[0003] The process of the dispersion method is to first disperse the pigment in a photosensitive resin to form a photosensitive resin composition, and then coat the photosensitive resin composition on a glass substrate, and obtain a specific pattern through exposure, development and other processes. After repeating the above coating, exposure and development processes three times, the pixel coloring pattern of red (R), green (G) and blue (B) in the color filter (hereinafter also referred to as "pixel layer") is obtained. Generally speaking, in order to further improve the contrast of the color filter, a black matrix (or light-shielding layer) is configured between the pixel coloring 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, and to expose at a high illumination for a short time at a low exposure of less than 50mJ / m2. In this case, the surface of the coating will cure quickly, but the bottom will not cure enough, resulting in poor linearity of the high-precision pattern.

[0005] Therefore, how to improve the linearity of a high-definition pattern of a pixel layer in a color filter formed by a photosensitive colored 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 colored resin composition, a color filter and a method for producing the same, and a liquid crystal display device, wherein a pixel layer produced using the photosensitive colored resin composition has good high-definition pattern linearity.

[0007] The present invention provides a photosensitive colored resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), wherein in an electron spin resonance spectrum of the photosensitive colored resin composition, a g value corresponding to a characteristic peak with the largest intensity is 1.990 to 2.020.

[0008] In one embodiment of the present invention, in the electron spin resonance spectrum of the photosensitive colored resin composition, the g value corresponding to the characteristic peak with the largest intensity is 1.995 to 2.015.

[0009] In one embodiment of the present invention, in the electron spin resonance spectrum of the photosensitive colored resin composition, the g value corresponding to the characteristic peak with the largest intensity is 2.000-2.010.

[0010] In one embodiment of the present invention, the colorant (A) includes at least one of zinc phthalocyanine dye (A-1) and halogenated phthalocyanine pigment (A-2).

[0011] In one embodiment of the present invention, the colorant (A) includes zinc phthalocyanine dye (A-1).

[0012] In one embodiment of the present invention, the zinc phthalocyanine dye (A-1) is a compound represented by formula (1),

[0013]

[0014] In formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a halogen atom or a group represented by formula (2), wherein A 1 ~A 16 At least one of them represents a basis represented by formula (2),

[0015] *-XA 17

[0016] Formula (2)

[0017] In formula (2), X represents a divalent linking group, A 17 represents a substituted or unsubstituted phenyl group, and * represents a bonding position.

[0018] In one embodiment of the present invention, the above-mentioned A 1 ~A 16 Six or more of them represent fluorine atoms.

[0019] The present invention provides a method for manufacturing a color filter, comprising: forming a pixel layer using the photosensitive colored resin composition as described above.

[0020] The invention provides a color filter, which is manufactured by the color filter manufacturing method as mentioned above.

[0021] The present invention provides a liquid crystal display device, comprising the color filter as described above.

[0022] Based on the above, the present invention provides a photosensitive colored resin composition, which can make the pixel layer have good high-definition pattern linearity because the g value corresponding to the characteristic peak with the highest intensity in the electron spin resonance spectrum is 1.990-2.020, and is therefore suitable for color filters and liquid crystal display devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is the electron spin resonance spectrum of Experimental Example 1. DETAILED DESCRIPTION

[0024] <Photosensitive Colored Resin Composition>

[0025] The present embodiment provides a photosensitive colored resin composition, including a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E). In addition, if necessary, the photosensitive colored resin composition of the present embodiment can selectively include an additive (F), or a combination thereof.

[0026] In this embodiment, the photosensitive colored resin composition is measured by an electron spin resonance (ESR) device. It is worth noting that the electron spin resonance is usually displayed as a g value, which is a function of the magnetic field intensity on the horizontal axis and the first 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.

[0027] The ESR signal can be used to observe the resonance phenomenon caused by the spin transition of unpaired electrons. The ESR signal means that there are unpaired electrons in the sample. In other words, the detection of the peak in the measurement waveform with the g value on the horizontal axis means the detection of unpaired electrons.

[0028] In the electron spin resonance spectrum of the photosensitive colored resin composition of this example, the g value corresponding to the characteristic peak with the largest intensity is 1.990 to 2.020, preferably 1.995 to 2.015, and more preferably 2.000 to 2.010.

[0029] When the g value is controlled within the above range, the pixel layer formed by the photosensitive color resin composition has good high-definition pattern linearity. On the contrary, when the g value is not within the above range, the high-definition pattern linearity of the pixel layer formed by the photosensitive color resin composition is poor. Although the detailed mechanism of this effect is not clear, it is speculated that the following factors are involved.

[0030] Generally speaking, when the exposure process is performed, the photoinitiator (radical photoinitiator) reacts to generate free radicals, causing free radical polymerization between the resin and the like, and the exposed part is hardened, and the hardened material remains even after development. 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 at the same time, the exposure is less than 50mJ / m 2 Under low exposure, high illumination is applied for a short time. In this case, the coating surface is cured quickly, but the bottom is not cured enough, resulting in poor linearity of high-definition patterns. In contrast, if the g value is controlled within a specific range, the unpaired electrons of zinc phthalocyanine dye (A-1) and the free radical photoinitiator will transfer energy, and the generation rate of free radicals is slow and continuous and intermittent, thereby reducing the curing speed of the coating surface and fully curing the bottom, effectively improving the problem of poor linearity of high-definition patterns.

[0031] The following will describe in detail the various components of the photosensitive colored resin composition used in this embodiment:

[0032] Hereinafter, “solid content of the photosensitive color resin composition” is the components excluding the solvent (E); and “the total weight of the solid content of the photosensitive color resin composition” is the total weight of the components excluding the solvent (E).

[0033] 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.

[0034] Colorant (A)

[0035] The colorant (A) of this embodiment may include at least one of zinc phthalocyanine dye (A-1) and halogenated phthalocyanine pigment (A-2). In another embodiment, the colorant (A) includes zinc phthalocyanine dye (A-1). In another embodiment, the colorant (A) may include other colorants (A-3) in addition to zinc phthalocyanine dye (A-1) and halogenated phthalocyanine pigment (A-2).

[0036] Zinc Phthalocyanine Dye (A-1)

[0037] The colorant (A) of this embodiment may include zinc phthalocyanine dye (A-1). When the colorant (A) includes zinc phthalocyanine dye (A-1), the pixel layer made of the photosensitive colored resin composition has better high-definition pattern linearity.

[0038] The zinc phthalocyanine dye (A-1) is not particularly limited, but is preferably a compound represented by formula (1).

[0039]

[0040] In formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a halogen atom or a group represented by formula (2), wherein A 1 ~A 16 At least one of them represents a group represented by formula (2).

[0041] *-XA 17

[0042] Formula (2)

[0043] In formula (2), X represents a divalent linking group, A 17 represents a substituted or unsubstituted phenyl group, and * represents a bonding position.

[0044] When the zinc phthalocyanine dye (A-1) is a compound represented by formula (1), the pixel layer produced by the photosensitive colored resin composition has better high-definition pattern linearity. Although the detailed mechanism of this effect is not clear, the following factors are presumed.

[0045] When zinc phthalocyanine dye (A-1) is a compound represented by formula (1), zinc phthalocyanine dye (A-1) is often present in the vicinity of photoinitiator (D) due to its high solubility in organic solvents. Energy transfer occurs from photoinitiator (D) to zinc phthalocyanine dye (A-1), and free radicals are generated slowly and continuously and intermittently, thereby further improving the problem of poor linearity of high-definition patterns.

[0046] (A 1 ~A 16 )

[0047] A 1 ~A 16 The halogen atom in A can be a fluorine atom, a chlorine atom, or a bromine atom. From the viewpoint that the pixel layer produced by the photosensitive coloring resin composition has more preferred high-definition pattern linearity, a fluorine atom is preferred. 1 ~A 16 Preferably, 6 or more fluorine atoms are present, more preferably 7 or more, and even more preferably 8 or more. Furthermore, preferably, 15 or less, more preferably, 12 or less, and even more preferably, 10 or less. 1 ~A 16 By setting the number of fluorine atoms in A to be greater than the above lower limit, the stability of the zinc phthalocyanine dye (A-1) and the high-definition pattern linearity of the pixel layer can be further improved. 1 ~A 16The number of fluorine atoms in the zinc phthalocyanine dye (A-1) is set to be below the above upper limit, which can further improve the affinity of the zinc phthalocyanine dye (A-1) with the solvent (E) in the photosensitive colored resin composition. The above upper limit and lower limit can be combined arbitrarily, for example, A 1 ~A 16 Preferably, 6 to 15 of the fluorine atoms are present, more preferably 7 to 12 of the fluorine atoms are present, and even more preferably 8 to 10 of the fluorine atoms are present.

[0048] (X)

[0049] In formula (2), X represents a divalent linking group. The divalent linking group is not particularly limited, and examples thereof include an oxygen atom, a sulfur atom, or -N(R a1 )-base (R a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms). Among these groups, X preferably represents an oxygen atom or a sulfur atom, and more preferably an oxygen atom, from the viewpoint of stability during subsequent baking.

[0050] (Substituents which may be present in the phenyl group)

[0051] In formula (2), A 17 represents a substituted or unsubstituted phenyl group. The phenyl ring in the phenyl group may have any substituent. The substituent is not particularly limited, and examples thereof include halogen atoms, alkyl groups, alkoxy groups (-OR A Base (R A represents an alkyl group)), an alkoxycarbonyl group (-COOR A Base (R A represents an alkyl group), an aryl group, an aryloxy group (-OR B Base (R B represents an aryl group)), an aryloxycarbonyl group (-COOR B Base (R B ( represents an aryl group)). Among these groups, an alkoxycarbonyl group is preferred from the viewpoint of development solubility or brightness.

[0052] The alkyl groups contained in these groups may be linear, branched, or cyclic. From the viewpoint of affinity with organic solvents, linear is preferred. The number of carbon atoms in the alkyl group is not particularly limited, and is generally 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less. By setting the number of carbon atoms in the alkyl group to be above the above lower limit, aggregation can be suppressed and the generation of foreign matter can be prevented. By setting the number of carbon atoms in the alkyl group to be below the above upper limit, solvent affinity and stability over time can be improved. The above upper and lower limits may be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 5, even more preferably 1 to 4, and particularly preferably 2 to 4. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, and hexyl. From the viewpoint of suppressing aggregation, the alkyl group is preferably methyl or ethyl, more preferably ethyl.

[0053] The aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The carbon number of the aryl group is not particularly limited, and is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. By setting the carbon number of the aryl group to be above the above lower limit, aggregation caused by steric repulsion can be suppressed. By setting the carbon number of the aryl group to be below the above upper limit, solvent affinity and stability over time can be improved. The above upper and lower limits can be arbitrarily combined. For example, the carbon number of the aryl group is preferably 4 to 12, more preferably 4 to 10, even more preferably 4 to 8, and particularly preferably 6 to 8.

[0054] The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Specific examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, and a heptalene ring.

[0055] The aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Specific examples of 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- 1,3-oxazole ring, isocyanate isoxazole ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indolering, isoindole ring, indolizine ring, 2H-1-benzopyran ring ring), 1H-2-benzopyran ring, quinolinering, isoquinoline ring, 4H-quinolidine ring, benzoimidazole ring, 1H-indazole ring, quinoline ring Quinoxaline ring, quinazoline ring, Cinnoline ring, phthalazine ring, 1,8- 1,8-naphthyridine ring, purine ring, and pteridine ring.

[0056] A in formula (2) 17In the formula (2), the benzene ring in the phenyl group may have any substituent. The number of the substituents is not particularly limited. From the viewpoint of improving heat resistance by generating π-π stacking of the colorant molecules and suppressing the decrease in brightness caused by the decomposition of the colorant, the number of substituents is preferably 1 for one benzene ring. In the case where the benzene ring in the phenyl group of the formula (2) has any substituent, the substitution position may be the ortho position, the meta position, or the para position. From the viewpoint of achieving the closest structure stacking, the substitution position is preferably the para position.

[0057] In formula (1), preferably A 1 ~A 16 More than 6 of them represent fluorine atoms. 1 ~A 16 When 6 or more of the atoms represent fluorine atoms, the pixel layer produced by the photosensitive color resin composition has more preferred high-definition pattern linearity.

[0058] In formula (1), A 1 ~A 16 In the formula (2), at least one of them represents a group. From the viewpoint of solubility in organic solvents or brightness, A is preferred. 1 ~A 4 wherein at least one of them is a group represented by formula (2), 5 ~A 8 wherein at least one of them is a group represented by formula (2), 9 ~A 12 At least one of them is a group represented by formula (2), and A 13 ~A 16 More than one of them is a group represented by formula (2); more preferably A 1 ~A 4 wherein two or more of them are groups represented by formula (2), 5 ~A 8 wherein two or more of them are groups represented by formula (2), 9 ~A 12 Two or more of them are groups represented by formula (2), and A 13 ~A 16 In the formula (2), at least two of them are groups. From the viewpoint of efficient stacking and suppression of brightness reduction, A is particularly preferred. 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 and A 15 is a group represented by formula (2), and A 1 , A 4 , A 5 , A 8 , A9 , A 12 , A 13 and A 16 A halogen atom.

[0059] Specific examples of the zinc phthalocyanine dye (A-1) may include, but are not limited to, at least one of the compounds represented by formula (1-1) to the compounds represented by formula (1-8).

[0060]

[0061]

[0062]

[0063] The zinc phthalocyanine dye (A-1) can be used alone or in combination of two or more.

[0064] The zinc phthalocyanine dye (A-1) can be prepared by a known method, for example, the method described in Japanese Patent Laid-Open No. 05-345861 can be used but is not limited thereto.

[0065] In this embodiment, based on 100 wt % of the total solid content of the photosensitive colored resin composition, the zinc phthalocyanine dye (A-1) may be 5 wt % to 80 wt %, preferably 10 wt % to 70 wt %, and more preferably 15 wt % to 50 wt %.

[0066] Halogenated phthalocyanine pigment (A-2)

[0067] Specific examples of the halogenated phthalocyanine pigment (A-2) include, but are not limited to, Color Index (CI) Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 62, CI Pigment Green 63.

[0068] At least one of JP2016-57635A, JP2018-36520A, and JP2017-111398A.

[0069] The halogenated phthalocyanine pigment (A-2) may preferably include CI Pigment Green 59.

[0070] The above-mentioned halogenated phthalocyanine pigment (A-2) can be used alone or in combination of two or more.

[0071] In this embodiment, based on 100 wt % of the total weight of the solid content of the photosensitive colored resin composition, the halogenated phthalocyanine pigment (A-2) may be 5 wt % to 80 wt %, preferably 10 wt % to 70 wt %, and more preferably 15 wt % to 50 wt %.

[0072] Other colorants (A-3)

[0073] In this embodiment, the colorant (A) may further include other colorants (A-3). Other colorants (A-3) may be inorganic pigments, organic pigments, or a combination thereof.

[0074] Inorganic pigments can be metal compounds such as metal oxides and metal zirconium salts. Among them, inorganic pigments can 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), antimony (Sb), composite oxides of the aforementioned metals, metal zirconium salts, or combinations thereof.

[0075] 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 67, 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: l, 57: 2, 58: 2, 58: 4, 60: l, 63: l, 63: 2, 64: l, 81: l, 83, 88, 90: l, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123 ,144,146,149,150,151,155,166,168,170,171,172,174,175,176,177,178,179,180,185,187,188,190,193,194,202,2 06, 207, 208, 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 42; CI Pigment Brown 23, 25, 28; CI Pigment Black 1, 7; or a combination thereof.

[0076] The other colorant (A-3) may preferably include CI Pigment Yellow 138, CI Pigment Blue 15:6, CI Pigment Blue 15:4, or a combination thereof.

[0077] The above-mentioned other coloring agents (A-3) may be used alone or in combination of two or more.

[0078] In this embodiment, based on 100 wt % of the total weight of the solid content of the photosensitive colored resin composition, the other colorant (A-3) may be 5 wt % to 40 wt %, preferably 5 wt % to 35 wt %, and more preferably 5 wt % to 30 wt %.

[0079] In this embodiment, based on 100 wt % of the total weight of the solid content of the photosensitive colored resin composition, the colorant (A) may be 5 wt % to 80 wt %, preferably 10 wt % to 70 wt %, and more preferably 15 wt % to 50 wt %.

[0080] In the photosensitive colored resin composition of the present embodiment, the colorant (A) is preferably used by dispersing it in a solvent through a dispersant. In the present embodiment, the dispersant can be appropriately selected from known dispersants. The dispersant can include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, silicone surfactants, fluorine surfactants and other surfactants, or a combination thereof. The above-mentioned dispersants can be non-polymer dispersants or polymer dispersants. From the perspective of being able to be evenly and finely dispersed, the surfactant is preferably a polymer dispersant.

[0081] Examples of polymer dispersants 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 their bases 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 three compounds selected from polyesters containing free carboxyl groups, polyamides or co-condensates of esters and amides (polyesteramides)), or combinations thereof.

[0082] The polymer dispersant is preferably a polymer dispersant having an amine value and containing a nitrogen atom in the main chain or a side chain, from the viewpoint of being able to preferably disperse the colorant (A) and having good dispersion stability.

[0083] Specific examples of the polymer dispersant containing a nitrogen atom in the main chain or the side chain are as follows.

[0084] 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).

[0085] Examples of commercially available products of polyurethanes include Disperbyk 161 (manufactured by BYK-Chemie).

[0086] Examples of commercially available products of unsaturated polyamides include Disperbyk 101 and Disperbyk 130 (manufactured by BYK-Chemie).

[0087] Commercially available products of the polyallylamine derivative include Ajisper PB821, Ajisper PB822, Ajisper PB824, and Ajisper PB827 (manufactured by Ajinomoto Fine-Techno Co., Ltd.).

[0088] Commercially available products of the polyethyleneimine derivative include Solsperse 33500 (manufactured by Lubrizol Corporation).

[0089] 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 EFKA 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, Japan); Ajisper PB711, Ajisper 823, Ajisper 880 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), etc.

[0090] The amount of the dispersant used is not particularly limited and can be appropriately adjusted according to needs.

[0091] Alkali soluble resin (B)

[0092] 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).

[0093] First alkali-soluble resin (B-1)

[0094] 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 other copolymerizable ethylenically unsaturated monomers (b-1-2).

[0095] The ethylenically unsaturated monomers (b-1-1) containing carboxylic acid groups may be used alone or in combination, and the ethylenically unsaturated monomers containing carboxylic acid groups include, but are not limited to, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid (MAA), crotonic acid, α-chloroacrylic acid, ethylacrylic acid, cinnamic acid, 2-acryloylethoxysuccinate, or 2-methacryloylethoxyethyl 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. The ethylenically unsaturated monomers containing carboxylic acid groups preferably 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.

[0096] In this embodiment, the usage amount of the carboxylic acid group-containing ethylenically unsaturated monomer (b-1-1) and other copolymerizable ethylenically unsaturated monomers (b-1-2) based on the first alkali-soluble resin (B-1) is 100 parts by weight, and the usage amount 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.

[0097] Other copolymerizable ethylenically unsaturated monomers (b-1-2) may 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); acrylate, referred to as MA), 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, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl 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 methacrylate, phenyl acrylate, phenyl methacrylate, triethylene glycol methoxy acrylate, triethylene glycol methoxy methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, eicosyl methacrylate, docosyl methacrylate, dicyclopentenyl oxyethyl acrylate (DCPOA); acrylate-nitrogen, nitrogen-dimethylaminoethyl, methacrylate-nitrogen, nitrogen-dimethylaminoethyl, acrylate-nitrogen, nitrogen-diethylaminopropyl, methacrylate-nitrogen, nitrogen-dimethylaminopropyl, acrylate-nitrogen, nitrogen-dibutylaminopropyl, nitrogen-methacrylate iso-butylaminoethyl; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate;Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether, etc.; nitrile 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. ;

[0098] 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.

[0099] In this embodiment, the amount of the carboxylic acid group-containing ethylenically unsaturated monomer (b-1-1) and other copolymerizable ethylenically unsaturated monomers (b-1-2) based on the first alkali-soluble resin (B-1) is 100 parts by weight, and the amount of other copolymerizable ethylenically unsaturated monomers (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.

[0100] 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 requirements. The polymerization method can be exemplified by solution polymerization. In addition to the required monomers, the reaction solution of the alkali-soluble resin (B) may also include a solvent, an initiator, and the like. The solvent may 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 etheracetate, referred to as PGMEA), 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 and ethyl 2-hydroxypropionate; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (ethyl 3-ethoxypropionate, referred to as 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, ethyl 2-methoxybutyrate and other esters; aromatic hydrocarbons such as toluene and xylene; amides such as nitrogen-methylpyrrolidone, nitrogen, nitrogen-dimethylformamide, or nitrogen, nitrogen-dimethylacetamide, etc. 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.

[0101] 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, referred to as AMBN); peroxide compounds such as dibenzoyl peroxide.

[0102] The first alkali-soluble resin (B-1) may be used alone or in combination of two or more.

[0103] 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).

[0104] In this embodiment, based on the total weight of the solid content of the photosensitive colored resin composition being 100 weight %, the first alkali-soluble resin (B-1) may be 5 weight % to 60 weight %, preferably 10 weight % to 55 weight %, and more preferably 15 weight % to 50 weight %.

[0105] Second alkali-soluble resin (B-2)

[0106] The second alkali-soluble resin (B-2) of this embodiment is prepared by polymerization of a mixture, and the mixture comprises an epoxy compound (b-2-1) having at least two epoxy groups and a compound (b-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. In addition, the mixture may further selectively comprise a carboxylic anhydride compound (b-2-3) and / or an epoxy-containing compound (b-2-4).

[0107] The epoxy compound (b-2-1) having at least two epoxy groups may have a structure as shown in the following formula (3-1) or the following formula (3-2). Here, the description of "the epoxy compound (b-2-1) may have a structure as shown in the following formula (3-1) or the following formula (3-2)" also covers the situation where a compound having a structure as shown in the following formula (3-1) and a compound having a structure as shown in the following formula (3-2) 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 (3-1):

[0108]

[0109] In formula (3-1),

[0110] R 1c、 R 2c、 R 3c and R 4c each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 12 carbon atoms, and R 1c、 R 2c、 R 3c and R 4c Each may be the same or different.

[0111] The epoxy compound (b-2-1) having at least two epoxy groups of the aforementioned formula (3-1) may include an epoxy group-containing bisphenol fluorene compound obtained by reacting a bisphenol fluorene compound with epihalohydrin, but is not limited thereto.

[0112] Specific examples of the bisphenol fluorene 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-fluoro ...chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene, 9,9-bis(4-hydroxy-3-bromo 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.

[0113] 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.

[0114] 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, etc.; (2) products manufactured by Osaka Gas Co., Ltd: such as PG-100, EG-210, etc.; (3) products manufactured by SMS Technology Co., Ltd: such as SMS-F9PhPG, SMS-F9CrG, SMS-F914PG; or combinations thereof.

[0115] Secondly, the epoxy compound (b-2-1) having at least two epoxy groups may also have a structure as shown in the following formula (3-2):

[0116]

[0117] In formula (3-2), 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 may be the same or different;

[0118] g represents an integer from 0 to 10.

[0119] The epoxy compound (b-2-1) having at least two epoxy groups of the above formula (3-2) is obtained, for example, by reacting a compound having the following formula (3-2-1) with a halide propylene oxide in the presence of an alkali metal hydroxide.

[0120]

[0121] In formula (3-2-1), R 5c To R 18c The definitions of g are respectively the same as R in formula (3-2) 5c To R 18c The definition of is the same as that of g and will not be repeated here.

[0122] Furthermore, the epoxy compound (b-2-1) having at least two epoxy groups of the aforementioned formula (3-2) is, for example, formed by a condensation reaction of a compound having the structure of the following formula (3-2-2) and phenol in the presence of an acid catalyst, and then, by adding an excess of halogenated propylene oxide to carry out a dehydrohalogenation reaction, the epoxy compound (b-2-1) having at least two epoxy groups as shown in formula (3-2) is obtained.

[0123]

[0124] In formula (3-2-2), 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 may be the same or different;

[0125] 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.

[0126] The aforementioned halogen atom is preferably chlorine or bromine, the aforementioned alkyl group may be, for example, methyl, ethyl or tert-butyl, and the aforementioned alkoxy group may be, for example, methoxy or ethoxy.

[0127] Specific examples of the above-mentioned 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, or cyclohexylcresol, etc. The above-mentioned phenols can generally be used alone or in combination.

[0128] Based on 1 mol of the compound having the structure of formula (3-2-2), the amount of the phenol is 0.5 mol to 20 mol, preferably 2 mol to 15 mol.

[0129] Specific examples of the acid catalyst include, but are not limited to, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminium chloride, zinc chloride, etc., among which p-toluenesulfonic acid, sulfuric acid or hydrochloric acid is preferred. The acid catalysts may be used alone or in combination.

[0130] In addition, although there is no particular limitation on the amount of the acid catalyst used, based on the amount of the compound having the structure of formula (3-2-2) being 100 weight percent (wt%), the amount of the acid catalyst used is preferably 0.1 wt% to 30 wt%.

[0131] The condensation reaction can be carried out without 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. The organic solvent can be used alone or in combination.

[0132] Based on the total amount of the compound having the structure of formula (3-2-2) and the phenols used being 100wt%, the amount of the organic solvent used being 50wt% to 300wt%, with 100wt% to 250wt% being preferred. In addition, the operating temperature of the condensation reaction is 40°C to 180°C, and the operating time of the condensation reaction is 1 hour to 8 hours.

[0133] After the condensation reaction is completed, a neutralization treatment or a water washing treatment may be performed. The neutralization treatment is to adjust the pH value of the solution after the reaction to pH 3 to pH 7, preferably pH 5 to pH 7. The water washing treatment may be performed using a neutralizer, which is an alkaline substance, and specific examples thereof 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 diethylene triamine, triethylene tetramine, aniline, and phenylene diamine; and ammonia, sodium dihydrogen phosphate, etc. The water washing treatment may be performed using a conventional method, for example, adding an aqueous solution containing a neutralizer to the solution after the reaction and repeatedly performing extraction. 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 (3-2-1).

[0134] Specific examples of the above-mentioned halogenated epoxypropane include, but are not limited to, 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane, or a combination thereof. Before the above-mentioned dehydrohalogenation reaction, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or during the reaction. The operating temperature of the above-mentioned dehydrohalogenation reaction is 20° C. to 120° C., and the operating time ranges from 1 hour to 10 hours.

[0135] In this embodiment, the alkali metal hydroxide added in the dehydrohalogenation reaction may also be an aqueous solution thereof. In this specific example, while the alkali metal hydroxide aqueous solution is continuously added to the dehydrohalogenation reaction system, water and halogenated propylene oxide may be continuously distilled out under reduced pressure or normal pressure, thereby separating and removing water, and halogenated propylene oxide may be continuously refluxed into the reaction system.

[0136] Before the dehydrohalogenation reaction, a quaternary ammonium salt such as tetramethyl ammonium chloride, tetramethyl ammonium bromide, or trimethylbenzyl ammonium chloride may be added as a catalyst, and the reaction may be carried out at 50° C. to 150° C. for 1 to 5 hours, and then an alkali metal hydroxide or an aqueous solution thereof may be added and the reaction may be carried out at 20° C. to 120° C. for 1 to 10 hours to carry out the dehydrohalogenation reaction.

[0137] Based on the total equivalent of hydroxyl groups in the compound having the structure of formula (3-2-1) being 1 equivalent, the amount of the halogenated propylene oxide used may 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 (3-2-1) being 1 equivalent, the amount of the alkali metal hydroxide added in the dehydrohalogenation reaction may be 0.8 to 15 equivalents, preferably 0.9 to 11 equivalents.

[0138] In addition, in order to make the above dehydrohalogenation reaction proceed smoothly, in addition to adding alcohols such as methanol and ethanol, aprotic polar solvents such as dimethyl sulfone and dimethyl sulfoxide can also be added to react. In the case of using alcohols, based on the total amount of the above halogenated propylene oxide being 100wt%, the amount of alcohol used can be 2wt% to 20wt%, preferably 4wt% to 15wt%. In the example of using aprotic polar solvents, based on the total amount of halogenated propylene oxide being 100wt%, the amount of aprotic polar solvent used can be 5wt% to 100wt%, among which 10wt% to 90wt% is preferred.

[0139] After the dehydrohalogenation reaction is completed, water washing treatment can be optionally performed. After that, the halogenated propylene oxide, alcohols and aprotic polar solvents are removed by heating and reducing pressure. The above-mentioned heating and reducing pressure is performed at a temperature of 110° C. to 250° C. and a pressure of 1.3 kPa (10 mmHg) or less.

[0140] In order to prevent the epoxy resin formed from containing hydrolyzable halogen, the solution after the dehydrohalogenation reaction can be added to a solvent such as toluene, methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to perform the dehydrohalogenation reaction again. In the dehydrohalogenation reaction, based on the total equivalent of hydroxyl groups in the compound having the structure of formula (3-2-1) being 1 equivalent, the amount of the alkali metal hydroxide used is 0.01 mol to 0.3 mol, preferably 0.05 mol to 0.2 mol. In addition, the operating temperature range of the dehydrohalogenation reaction is 50°C to 120°C, and the operating time range is 0.5 hours to 2 hours.

[0141] After the dehydrohalogenation reaction is completed, the salts are removed by filtering and washing. In addition, the 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 (3-2). The epoxy compound (b-2-1) having at least two epoxy groups of the above formula (3-2) 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.

[0142] The compound (b-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is selected from the group consisting of (1) to (3) below: (1) acrylic acid, methacrylic acid, 2-methacryloyloxyethylbutanedioic acid acid), 2-methacryloyloxybutylsuccinic acid, 2-methacryloyloxyethyl adipic acid, 2-methacryloyloxybutyl adipic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxypropyl maleic acid, 2-methacryloyloxybutyl maleic acid, 2-methacryloyloxypropylsuccinic acid, 2-methacryloyloxypropyl adipic acid, 2-methacryloyloxypropyl tetrahydrophthalic acid, 2-methacryloyloxypropyl phthalic acid, 2-methacryloyloxybutyl phthalic acid, or 2-methacryloyloxybutyl hydrogen phthalic 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, wherein the hydroxyl-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) acrylate), 4-hydroxybutyl methacrylate ((4-hydroxybutyl) methacrylate), or pentaerythritol trimethacrylate, etc. In addition, the carboxylic acid anhydride compound described herein may be the same as the carboxylic acid 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 herein.

[0143] The mixture of the second alkali-soluble resin (B-2) may further selectively 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) may be selected from the group consisting of the following (1) to (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. Tetracarboxylic acid anhydride compounds such as tetracarboxylicdianhydride (BTDA for short), diphenylene tetracarboxylic dianhydride or diphenyl ether tetracarboxylic dianhydride.

[0144] The epoxy group-containing compound (b-2-4) is, for example, selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, unsaturated glycidyl ether compounds, epoxy group-containing unsaturated compounds, or any combination thereof. The unsaturated glycidyl ether compounds include, but are 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.).

[0145] The second alkali-soluble resin (B-2) can be obtained by polymerization reaction of an epoxy compound (b-2-1) having at least two epoxy groups of formula (3-1) and 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 above-mentioned 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 equivalent to 1 equivalent, and more preferably 0.75 equivalent to 1 equivalent. When a plurality of 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, and more preferably 5 / 95 to 80 / 20. In addition, the operating temperature range of the above reaction is, for example, in the range of 50°C to 130°C.

[0146] The second alkali-soluble resin (B-2) can be obtained by reacting an epoxy compound (b-2-1) having at least two epoxy groups of formula (3-2) 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, and then adding a carboxylic anhydride compound (b-2-3) and / or an epoxy-containing compound (b-2-4) for polymerization. The total equivalent of epoxy groups on the epoxy compound (b-2-1) having at least two epoxy groups of formula (3-2) is 1 equivalent, and the acid value equivalent of the compound (b-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is preferably 0.8 equivalents to 1.5 equivalents, and more preferably 0.9 equivalents to 1.1 equivalents. Based on the total amount of hydroxyl groups in the above-mentioned 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 %.

[0147] When preparing the second alkali-soluble resin (B-2), in order to accelerate the reaction, an alkaline compound is usually added to the reaction solution as a reaction catalyst. The reaction catalyst can be used alone or in combination, and the reaction catalyst includes but is not limited to: triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine, tetramethyl ammonium chloride, benzyltriethyl ammonium chloride, etc. Based on the total amount of the epoxy compound (b-2-1) having at least two epoxy groups and the compound (b-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group used being 100 parts by weight, the amount of the reaction catalyst used is preferably 0.01 to 10 parts by weight, and more preferably 0.3 to 5 parts by weight.

[0148] In addition, in order to control the degree of polymerization, a polymerization inhibitor is usually added to the reaction solution. The above-mentioned polymerization inhibitor may include, but is not limited to: methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol or phenothiazine. In general, the above-mentioned polymerization inhibitors can be used alone or in combination. Based on the total amount of the epoxy compound (b-2-1) having at least two epoxy groups and the compound (b-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group used being 100 parts by weight, the amount of the polymerization inhibitor used is preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight.

[0149] 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; or dialkyl glycol ethers; or ethyl 3-ethoxypropionate. The above-mentioned polymerization reaction solvents can generally be used alone or in combination. In addition, the acid value of the above-mentioned second alkali-soluble resin (B-2) is preferably 50 mgKOH / g to 200 mgKOH / g, and more preferably 60 mgKOH / g to 150 mgKOH / g.

[0150] 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 gel permeation chromatography.

[0151] The second alkali-soluble resin (B-2) may be used alone or in combination of two or more.

[0152] In this embodiment, based on the total weight of the solid content of the photosensitive colored resin composition as 100 weight%, the second alkali-soluble resin (B-2) may be 5 weight% to 60 weight%, preferably 10 weight% to 55 weight%, and more preferably 15 weight% to 50 weight%.

[0153] In this embodiment, based on 100 wt % of the total weight of the solid content of the photosensitive colored resin composition, the alkali-soluble resin (B) may be 5 wt % to 60 wt %, preferably 10 wt % to 55 wt %, and more preferably 15 wt % to 50 wt %.

[0154] Photopolymerizable compound (C)

[0155] The photopolymerizable compound (C) of the present embodiment may include an unsaturated compound having at least one ethylenically unsaturated group and an unsaturated compound having at least two ethylenically unsaturated groups.

[0156] Specific examples of the unsaturated compound having at least one ethylenically unsaturated group include, but are not limited to, acrylamide, acryloyl morpholine, methacryloyl morpholine, 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, methacrylic acid Tetrachlorophenyl acrylate, 2-tetrachlorophenoxyethyl acrylate, 2-tetrachlorophenoxyethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, tetrabromophenyl acrylate, tetrabromophenyl methacrylate, 2-tetrabromophenoxyethyl acrylate, 2-tetrabromophenoxyethyl methacrylate, 2-trichlorophenoxyethyl acrylate, 2-trichlorophenoxyethyl methacrylate, tribromophenyl acrylate, tribromophenyl methacrylate, 2-tribromophenoxyethyl acrylate, 2-tribromophenoxyethyl methacrylate, 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. Among them, the unsaturated compound having at least one ethylenically unsaturated group can be used alone or in combination.

[0157] 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 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, tetraacrylate ditrimethylolpropane, tetramethacrylate ditrimethylolpropane, 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 a model number of TO-1382, or a product manufactured by Nippon Kayaku Co., Ltd. with a model number of KAYARAD DPCA-12, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120, etc. Among them, the unsaturated compound having at least two ethylenically unsaturated groups can be used alone or in combination. ,

[0158] Specific examples of the photopolymerizable compound (C) 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.

[0159] As a specific example of the photopolymerizable compound (C), dipentaerythritol hexaacrylate, dipentaerythritol tetraacrylate, or a combination thereof is more preferable.

[0160] The photopolymerizable compound (C) may be used alone or in combination of two or more.

[0161] In this embodiment, based on 100 wt % of the total weight of the solid content of the photosensitive colored resin composition, the photopolymerizable compound (C) may be 5 wt % to 60 wt %, preferably 8 wt % to 55 wt %, and more preferably 10 wt % to 50 wt %.

[0162] Photoinitiator (D)

[0163] The photoinitiator (D) of this embodiment may be a free radical photoinitiator.

[0164] Examples of the photoinitiator (D) include acetophenone compounds, biimidazole compounds, acyl oxime compounds, or combinations thereof.

[0165] 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-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N,N-di-methylamino-1-(4-morpholinophenyl)-1-butanone, or a combination thereof.

[0166] 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, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl-biimidazole, Phenyldiimidazole (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 (2,2'-bis(o-ethylphenyl)-4, 4',5,5'-tetraphenyl-biimidazole), 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, etraphenyl-biimidazole), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole), 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole, or a combination thereof.

[0167] The acyl oxime compound is selected from ethane ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime), such as CGI-242 manufactured by Ciba Specialty Chemicals, whose structure is shown in the following formula (4-1), 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime), such as Ciba Specialty Chemicals, which is a product of CGI-242, whose structure is shown in the following formula (4-1)), Chemicals) with the trade name CGI-124, whose structure is shown in the following formula (4-2)), ethane ketone, 1-[9-ethyl-6-(2-chloro-4-benzyl-thio-benzoyl)-9H-carbazole-3-substituent]-, 1-(oxy-acetyloxime) (Ethanone, 1-[9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime), such as manufactured by Asahi Denka Co., Ltd., whose structure is shown in the following formula (4-3)), or a combination thereof.

[0168]

[0169] In a specific example, the photoinitiator (D) may further include benzophenone compounds such as thioxanthone, 2,4-diethyl-thioxanthanone, thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc.; α-diketone compounds such as benzil and acetyl; acyloin compounds such as benzoin; benzoinmethylether, benzoinethylether, benzoinisopropylether, etc. 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-tert-butylperoxide. Among them, benzophenone compounds are preferred, and 4,4'-bis(diethylamino)benzophenone is the best.

[0170] The photoinitiator (D) preferably includes 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime) (for example, a commercial product manufactured by Ciba Specialty Chemicals under the trade name CGI-124).

[0171] The above-mentioned photoinitiators (D) may be used alone or in combination of two or more.

[0172] In this embodiment, based on 100 wt % of the total weight of the solid content of the photosensitive colored resin composition, the photoinitiator (D) may be 0.1 wt % to 12 wt %, preferably 0.5 wt % to 11 wt %, and more preferably 1 wt % to 10 wt %.

[0173] Solvent (E)

[0174] The preparation of the photosensitive colored resin composition of this embodiment is usually to dissolve the components other than the colorant (A) in a solvent (E) to prepare a liquid composition, and then add the colorant (A) and mix them evenly. The solvent (E) needs to be selected to dissolve the alkali-soluble resin (B), the photopolymerizable compound (C), and the photoinitiator (D), and needs to be non-reactive with these components and have appropriate volatility. In addition, when the additive (F) is added, the solvent (E) needs to be selected to dissolve the additive (F), and needs to be non-reactive with these components and have appropriate volatility.

[0175] In addition, the solvent (E) may be the same as the solvent used to prepare the alkali-soluble resin (B), which will not be described in detail. The solvent may be used alone or in combination. The solvent (E) preferably includes propylene glycol methyl ether acetate, 3-ethoxyethyl propionate, or a combination thereof.

[0176] In this embodiment, based on 100 wt % of the total weight of the photosensitive colored 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 %.

[0177] Additives (F)

[0178] In this embodiment, the photosensitive colored 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.

[0179] Examples of fillers include glass, aluminum, or a combination thereof.

[0180] Examples of the polymer compound include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and combinations thereof.

[0181] Examples of the adhesion promoter include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidol propyl trimethoxysilane, 3-glycidol propyl methyl dimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-chloropropyl methyl dimethoxysilane, 3-chloropropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-thiol propyl trimethoxysilane, or a combination thereof.

[0182] Examples of the antioxidant include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or a combination thereof.

[0183] Examples of the ultraviolet absorber include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxyphenone, or a combination thereof.

[0184] As the anti-agglomeration agent, sodium polyacrylate can be mentioned.

[0185] The above-mentioned additives (F) may be used alone or in combination.

[0186] The additive (F) is preferably 3-thiolpropyltrimethoxysilane, 2,2-thiobis(4-methyl-6-tert-butylphenol), or a combination thereof.

[0187] In this embodiment, based on 100 wt % of the total weight of the photosensitive colored resin composition, the additive (F) may be 10 wt % or less, preferably 7 wt % or less, and more preferably 5 wt % or less.

[0188] <Method for preparing photosensitive colored resin composition>

[0189] The preparation method of the photosensitive colored resin composition of this embodiment is not particularly limited. Specifically, the preparation method of the photosensitive colored resin composition can be listed as follows: (1) First, a colorant (A) is added to a solvent (E) to prepare a pigment dispersion, and then an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and an additive (F) used as needed are added to the pigment dispersion and mixed; (2) A colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and an additive (F) used as needed are added to a solvent (E) at the same time and mixed; (3) A method in which an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and an additive (F) used as required 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 pigment dispersion, and then another portion of an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and an additive (F) used as required are added to the pigment dispersion and mixed, etc.

[0190] Among these methods, the methods (1) and (4) are preferred from the viewpoint of being able to effectively prevent the aggregation of the pigment and achieve uniform dispersion.

[0191] The method for uniformly dispersing / uniformly mixing the components can be exemplified by mixing and / or dispersing using a stirrer and / or a dispersing machine. The dispersing machine can be exemplified by roller mills such as a double roll mill and a triple roll mill, ball mills such as a ball mill and a vibrating ball mill, a paint conditioner, a continuous disk type bead mill, a continuous ring type bead mill, and the like. The bead mill dispersion condition is preferably such that the bead diameter used is preferably 0.03 mm to 2.00 mm, and more preferably 0.10 mm to 1.0 mm.

[0192] <Method for Manufacturing Color Filter>

[0193] The method for manufacturing the color filter of this embodiment includes forming a pixel layer using the photosensitive colored resin composition as described above. Specifically, the photosensitive colored resin composition mixed into a solution state is coated on a substrate mainly by a coating method such as rotary coating, cast coating, ink-jet coating or roller coating. After coating, most of the solvent is removed by vacuum drying, and then the solvent is removed by pre-baking to form a pre-baked coating film. Among them, the conditions of vacuum drying and pre-baking vary depending on the type and proportion of each component. Generally, vacuum drying is carried out at a pressure of 0 to 200 mmHg for 1 second to 60 seconds, and pre-baking is carried out at a temperature of 70 to 110°C for 1 minute to 15 minutes. After pre-baking, the pre-baked coating film is exposed under a specified photomask, immersed in a developer at a temperature of 23±2°C for 15 seconds to 5 minutes for development, and the unwanted parts are removed 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.

[0194] Specific examples of the aforementioned substrate include: alkali-free glass, soda-lime glass, hard glass (Pyles glass), quartz glass, soda glass, or a substrate with a transparent conductive film attached to such glass for liquid crystal display devices; or a photoelectric conversion device substrate (such as a silicon substrate) for solid-state imaging devices, etc. Such substrates generally form a black matrix that isolates each pixel layer.

[0195] Furthermore, specific examples of the developer include an alkaline aqueous solution composed of at least one of the alkaline compounds 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, 1,8-diazabicyclo[5.4.0]-7-undecene, etc., and the concentration thereof is generally 0.001 to 10% by weight, preferably 0.005 to 5% by weight, and more preferably 0.01 to 1% by weight.

[0196] When the developer composed of the 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.

[0197] The air-dried substrate with the photocurable coating layer is heated at a temperature of 100 to 280°C for 1 to 15 minutes using a heating device such as a hot plate or an oven to remove the volatile components in the coating and to allow the unreacted ethylenic unsaturated double bonds in the coating to undergo a thermal curing reaction. The same process is repeated three times on predetermined pixels using photosensitive resin compositions of various colors (mainly including red, green, and blue) to obtain red, green, and blue pixel layers.

[0198] 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.

[0199] Furthermore, the liquid crystal alignment film used above is used to limit the alignment of liquid crystal molecules, and is not particularly limited here, and can be 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.

[0200] <Liquid Crystal Display Device>

[0201] The liquid crystal display device of this specific example includes a color filter substrate containing a color filter made by the manufacturing method of the color filter as described above; and a driving substrate provided with a thin film transistor (TFT). The liquid crystal display device of this embodiment is arranged oppositely with a gap (cell gap) inserted between the above two substrates, and the surrounding parts of the two substrates are bonded with a sealant, and the liquid crystal is filled and injected into the gap divided by the substrate surface and the sealant, and the injection hole is sealed to form a liquid crystal cell. Then, a polarizing plate is bonded to the outer surface of the liquid crystal cell, that is, the other side surfaces of each substrate constituting the liquid crystal cell to obtain a liquid crystal display device.

[0202] As for the liquid crystal used above, that is, the liquid crystal compound or the liquid crystal composition, there is no particular limitation here, but any liquid crystal compound and liquid crystal composition can be used.

[0203] 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 limitations on the implementation of the present invention.

[0204] Synthesis Example of Alkali-Soluble Resin (B)

[0205] Synthesis Example B-1

[0206] 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, and the interior of the flask was filled with nitrogen. After that, the mixture was slowly stirred and heated to 80°C to uniformly mix the reactants and perform polymerization for 4 hours. After that, the mixture was heated to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile was added and polymerized for 1 hour to obtain the first alkali-soluble resin of Synthesis Example B-1.

[0207] Synthesis Example B-2

[0208] 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, and the interior of the flask was filled with nitrogen. After that, the mixture was slowly stirred and heated to 80°C to uniformly mix the reactants and polymerize for 3 hours. After that, the mixture was heated to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile was added and polymerized for 1 hour to obtain the first alkali-soluble resin of Synthesis Example B-2.

[0209] Experimental Examples 1 to 10 and Comparative Examples 1 to 11

[0210] Experimental Examples 1 to 10 and Comparative Examples 1 and 2 of the photosensitive colored resin composition are described below:

[0211] Experimental Example 1

[0212] First, 27.5 parts by weight of the compound represented by formula (1-1) (i.e., colorant (A-1-1)), 15 parts by weight of CI Pigment Yellow 138 (i.e., colorant (A-3-1)), 400 parts by weight of propylene glycolmethyl 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, and the mixture was pre-pulverized for 1 hour using a paint shaker (PCMH-C50M, manufactured by Asada Steel). The solution was then 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 for 20 hours using a paint shaker to obtain a colorant dispersion of Experimental Example 1.

[0213] Next, 442.5 parts by weight of the above-mentioned colorant dispersion (containing 27.5 parts by weight of the colorant (A-1-1) and 15 parts by weight of the colorant (A-3-1)), 45 parts by weight of the alkali-soluble resin of Synthesis Example B-1, 10 parts by weight of dipentaerythritol hexaacrylate (i.e., photopolymerizable compound (C-1)), and 2.5 parts by weight of 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime) (i.e., photoinitiator (D-1) (trade name OXE-01, manufactured by BASF)) 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)), and the mixture was stirred uniformly with a shaking type stirrer to obtain a photosensitive color resin composition of Experimental Example 1.

[0214] The photosensitive colored resin composition of Experimental Example 1 thus prepared was evaluated in the evaluation method described later. The results are shown in Table 1.

[0215] Experimental Examples 2 to 10, Comparative Examples 1 and 2

[0216] The preparation of the photosensitive coloring resin composition of Experimental Examples 2 to 10, Comparative Example 1, and Comparative Example 2 was prepared by the same process as that of Experimental Example 1, and the difference was that the types of components and the amounts used of the photosensitive coloring resin composition were changed. Among them, 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 prepared photosensitive coloring resin composition was evaluated in the evaluation method described below, and the results of Experimental Examples 2 to 10, Comparative Example 1, and Comparative Example 2 are shown in Table 1, respectively.

[0217]

[0218] [Table 2]

[0219]

[0220] [Evaluation method]

[0221] a. Electron Spin Resonance (ESR)

[0222] The photosensitive colored resin compositions of the experimental examples and comparative examples were sealed in the innermost part of a sample tube (quartz, manufactured by JEOL Ltd., for X-Band, 100 mm) filled with nitrogen, and then nitrogen was refilled, and 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 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.

[0223] The measurement conditions of the electron spin resonance device are as follows:

[0224] Microwave power: 15m W;

[0225] Modulated magnetic field: 0.6m T;

[0226] Response: 0.02 seconds;

[0227] Magnetic field: 351.4 mT;

[0228] Magnetic field scanning width: ±5m T;

[0229] Increase rate: 500.

[0230] b. Linearity of high-definition patterns

[0231] The photosensitive colored resin compositions of the experimental examples and the comparative examples were each applied by spin coating on a glass substrate having a length and width of 100 mm. 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 having a film thickness of 2.5 μm. Afterwards, an exposure machine (manufactured by Canon, model PLA-501F) was used to expose the glass substrate at 50 mJ / cm2 through a photomask having a stripe pattern of 25 μm (pitch 50 μm). 2 ) 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. Thereafter, the pre-baked coating was washed with pure water and post-baked at 200°C for 80 minutes to form a photosensitive resin layer with a stripe pattern (hereinafter also referred to as a "pixel layer" or "pattern") having a film thickness of 2.0 microns on the glass substrate.

[0232] The stripe pattern formed by the above method was observed using an optical microscope to determine the ratio (L) of the pattern with good linearity, and the linearity of the pattern with high definition was evaluated based on the following criteria.

[0233] ◎: L≧90%;

[0234] ○: 80% ≤ L < 90%;

[0235] △: 70% ≦ L < 80%;

[0236] ×: L<70%.

[0237] <Evaluation Results>

[0238] It can be seen from Table 1 that when the g value corresponding to the characteristic peak with the largest intensity is between 1.990 and 2.020 (Experimental Examples 1 to 10), the pixel layer made of the photosensitive colored resin composition has good high-definition pattern linearity.

[0239] On the contrary, when the g value corresponding to the characteristic peak with the highest intensity is not in the range of 1.990 to 2.020 (Comparative Examples 1 and 2), the high-definition pattern of the pixel layer made of the photosensitive colored resin composition has poor linearity.

[0240] When the colorant (A) in the photosensitive colored resin composition includes the compound represented by formula (1) (ie, zinc phthalocyanine dye (A-1)) (Experimental Examples 1 to 6, 8 to 10), the pixel layer made of the photosensitive colored resin composition has better high-definition pattern linearity.

[0241] When A in formula (1) 1 ~A 16 When 6 or more of the atoms represent fluorine atoms (Experimental Examples 1 to 3, 8 to 10), the pixel layer produced by the photosensitive colored resin composition has more preferable high-definition pattern linearity.

[0242] In summary, the present invention provides a photosensitive colored resin composition, which can make the pixel layer have good high-definition pattern linearity because the g value corresponding to the characteristic peak with the largest intensity in the electron spin resonance spectrum is 1.990-2.020, and is therefore suitable for color filters and liquid crystal display devices.

[0243] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A photosensitive colored resin composition comprising: Colorant (A); Alkali soluble resin (B); A photopolymerizable compound (C); Photoinitiator (D); as well as Solvent (E), In the electron spin resonance spectrum of the photosensitive colored resin composition, the g value corresponding to the characteristic peak with the largest intensity is 1.990 to 2.

020.

2. The photosensitive colored resin composition according to claim 1, wherein In the electron spin resonance spectrum of the photosensitive colored resin composition, the g value corresponding to the characteristic peak with the largest intensity is 1.995 to 2.

015.

3. The photosensitive colored resin composition according to claim 1, wherein In the electron spin resonance spectrum of the photosensitive colored resin composition, the g value corresponding to the characteristic peak with the largest intensity is 2.000 to 2.

010.

4. The photosensitive colored resin composition according to claim 1, wherein The colorant (A) includes at least one of a zinc phthalocyanine dye (A-1) and a halogenated phthalocyanine pigment (A-2).

5. The photosensitive colored resin composition according to claim 1, wherein The colorant (A) includes zinc phthalocyanine dye (A-1).

6. The photosensitive colored resin composition according to claim 4 or 5, wherein The zinc phthalocyanine dye (A-1) is a compound represented by formula (1), In formula (1), A 1 ~A 16 Each independently represents a hydrogen atom, a halogen atom or a group represented by formula (2), wherein A 1 ~A 16 At least one of the groups is represented by formula (2), *——X——A17 Formula (2) In formula (2), X represents a divalent linking group, A 17 represents a substituted or unsubstituted phenyl group, and * represents a bonding position.

7. The photosensitive colored resin composition according to claim 6, wherein A 1 ~A 16 Six or more of them represent fluorine atoms.

8. A method for manufacturing a color filter, comprising: A pixel layer is formed using the photosensitive colored 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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