Method for manufacturing color filter, color filter, and liquid crystal display device

Abstract

The invention provides a manufacturing method of a color filter, the color filter and a liquid crystal display device. A colored layer (pattern) in the color filter manufactured by the manufacturing method of the color filter has a good after-baking residual film rate. The manufacturing method of the color filter comprises the following steps: coating a photosensitive colored resin composition on a substrate to obtain a coating film; performing exposure treatment on the coating film with ultraviolet rays through a photomask; carrying out developing treatment on the exposed coating film by using a developing solution so as to obtain a pattern; and performing post-baking treatment on the pattern in a temperature range of 200 DEG C to 250 DEG C for 1 to 15 minutes. The photosensitive colored resin composition includes a pigment (A), an alkali-soluble resin (C), a photopolymerizable compound (D), a photoinitiator (E), and a solvent (F), in which the pigment (A) includes a pigment (A-1), and the pigment (A-1) is a compound represented by formula (1). # imgabs0 #

Description

Technical Field

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

[0002] Color display devices using color filters include (i) color liquid crystal display devices, which include: a combination of a backlight as a light source, a liquid crystal as an optical shutter, and a color filter having a color adjustment function (color conversion function, color separation function, color correction function, etc.); and (ii) color organic electroluminescent (EL) display devices, which include: a combination of a synthetic white organic electroluminescent (EL) light source and a color filter having a color adjustment function (color conversion function, color separation function, color correction function, etc.). Color filters can also be used in image sensors such as complementary metal-oxide-semiconductor (CMOS) and charge-coupled device (CCD).

[0003] At present, the known methods for manufacturing color filters include electro-deposition, printing, and photolithography. Electro-deposition is to pre-form a transparent electrode with a specified pattern; a resin containing a pigment dissolved or dispersed in a solvent is ionized by applying a voltage to form a pattern. Printing is a printing method such as offset printing using ink containing a thermosetting resin or a UV curing resin. Photolithography is to use a photosensitive colored resin composition in which a colorant such as a pigment or dye is dispersed or dissolved in a photoresist material. In recent years, photolithography has become the mainstream method for manufacturing color filters.

[0004] When a color filter is formed using a lithography process, for example, a coating film of a negative photosensitive colored resin composition is formed on a substrate, and then the coating film is exposed to ultraviolet light through a photomask having a predetermined opening pattern, and then the unexposed portion is dissolved and removed by development to form a pattern (for example: Patent Document 1).

[0005] However, although various methods for manufacturing color filters have been developed, the color layer (pattern) in the color filter formed by the photosensitive color resin composition has the disadvantage of poor post-baking residual film rate, and a relatively large amount of photosensitive color resin composition is required to prepare the color layer (pattern), thereby failing to achieve the effect of saving resources and being environmentally friendly.

[0006] [Patent Document]

[0007] [Patent Document 1] JP H2-144502-A

[0008] Therefore, how to improve the post-baking residual film rate of the colored layer (pattern) in the color filter formed by the photosensitive colored resin composition is a problem that the technicians in this field are eager to solve. Summary of the invention

[0009] The present invention provides a method for manufacturing a color filter, a color filter, and a liquid crystal display device, wherein the color layer (pattern) in the color filter manufactured by the method for manufacturing the color filter has a good post-baking residual film rate.

[0010] The present invention provides a method for manufacturing a color filter, comprising: applying a photosensitive colored resin composition on a substrate to obtain a coating film; exposing the coating film with ultraviolet light through a photomask; developing the exposed coating film with a developer to obtain a pattern; and post-baking the pattern at a temperature range of 200° C. to 250° C. for 1 minute to 15 minutes. The photosensitive colored resin composition comprises a pigment (A), an alkali-soluble resin (C), a photopolymerizable compound (D), a photoinitiator (E), and a solvent (F), wherein the pigment (A) comprises a pigment (A-1), and the pigment (A-1) is a compound represented by formula (1).

[0011]

[0012] In formula (1),

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

[0014] B q- It represents a heteropoly acid anion with a valence of q;

[0015] R 1 , R 2 , R 3 , R 4 , and R 5 Each independently represents a hydrogen atom, or a substituted or unsubstituted alkyl group, wherein R 2 , R 3 , R 4 , and R5 At least one of them is a substituted or unsubstituted alkyl group, R 2 With R 3 Can bond to each other to form a ring structure, R 4 With R 5 Can bond to each other to form a ring structure, multiple R 1 , R 2 , R 3 , R 4 , and R 5 Each may be the same or different;

[0016] R 6 and R 7 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a halogen atom, or a cyano group;

[0017] Ar represents a substituted or unsubstituted divalent aromatic group, and multiple Ars may be the same or different;

[0018] p and q represent integers greater than 2;

[0019] r and s represent an integer greater than 1;

[0020] v represents 0 or 1. When v represents 0, there is no bond;

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

[0022] t+v and u+v are integers of 0 or more and 4 or less.

[0023] In one embodiment of the present invention, the above R 2 , R 3 , R 4 , and R 5 Each independently represents a substituted or unsubstituted alkyl group.

[0024] In one embodiment of the present invention, the above-mentioned B q- In the embodiment, the heterogeneous polyacid anions contain at least one of molybdenum (Mo) and tungsten (W).

[0025] In one embodiment of the present invention, the post-baking treatment lasts for 3 minutes to 10 minutes.

[0026] In one embodiment of the present invention, the photosensitive colored resin composition further comprises a dye (B), wherein the dye (B) comprises a dye (B-1), wherein the dye (B-1) is a compound represented by formula (2),

[0027]

[0028] In formula (2),

[0029] R 8 , R 9 , R 10 , and R 11 Each independently represents a hydrogen atom, -L 1 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L 1 、-OH、-OL 1 、-SO 3 - 、-SO 3 H, -SO 3 M, -COOH, -COOL 1 、-SO 3 L 1 、-SO 2 NHL 2 or -SO 2 NL 2 L 3 A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms;

[0030] R 12 Indicates -SO 3 - 、-SO 3 H, -SO 3 M, -COOH, -COOL 1 、-SO 3 L 1 、-SO 2 NHL 2 or -SO 2 NL 2 L 3 ;

[0031] m represents an integer from 0 to 5; when m represents 2 to 5, multiple R 12 Each may be the same or different;

[0032] X represents a halogen atom;

[0033] n represents 0 or 1;

[0034] L 1 represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted by a halogen atom, wherein -CH 2 - unsubstituted or substituted by -O-, carbonyl or -NL 4 -replace;

[0035] L 4 represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom;

[0036] L 2 and L 3 Each independently represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q; wherein the hydrogen atoms in the linear alkyl group having 1 to 10 carbon atoms, the branched alkyl group having 3 to 10 carbon atoms, or the cycloalkyl group having 3 to 30 carbon atoms are unsubstituted or substituted with a substituent selected from the group consisting of a hydroxyl group, a halogen atom, -Q, -CH=CH 2 and -CH=CH-L 1 The group consisting of: -CH in a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 3 to 30 carbon atoms 2 - unsubstituted or substituted by -O-, carbonyl or -NL 4 - replace; or

[0037] L 2 With L 3 bonded to each other to form a heterocyclic group having 1 to 10 carbon atoms, wherein the hydrogen atoms in the heterocyclic group having 1 to 10 carbon atoms are unsubstituted or replaced by L 1 , -OH, or -Q;

[0038] Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, a heteroaromatic group having 5 to 10 carbon atoms, a halogen atom, -L 1 、-OH、-OL 1 、-NO 2 、-CH=CH 2 or -CH=CH-L 1 A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or a substituted halogen atom, -L 1 、-OH、-OL 1 、-NO 2 、-CH=CH 2 or -CH=CH-L 1 a substituted heteroaromatic group having 5 to 10 carbon atoms;

[0039] M represents potassium or sodium.

[0040] In one embodiment of the present invention, based on 100 parts by weight of the alkali-soluble resin (C), the pigment (A-1) is 1 part by weight to 300 parts by weight; and based on the total weight of the solid content of the photosensitive colored resin composition being 100% by weight, the pigment (A-1) is 0.5% by weight to 50% by weight.

[0041] In one embodiment of the present invention, based on 100 parts by weight of the alkali-soluble resin (C), the dye (B) is 1 to 90 parts by weight, and the dye (B-1) is 1 to 90 parts by weight; and based on the total weight of the solid content of the photosensitive colored resin composition being 100% by weight, the dye (B) is 0.1 to 20% by weight, and the dye (B-1) is 0.1 to 20% by weight.

[0042] In one embodiment of the present invention, based on 100 parts by weight of the alkali-soluble resin (C), 100 parts by weight of the alkali-soluble resin (C), 1 part by weight to 300 parts by weight of the pigment (A), 30 parts by weight to 450 parts by weight of the photopolymerizable compound (D), 2 parts by weight to 20 parts by weight of the photoinitiator (E), and 500 parts by weight to 5000 parts by weight of the solvent (F); and based on the total weight of the solid content of the photosensitive colored resin composition being 100% by weight, the pigment (A) is 0.5% by weight to 50% by weight, the alkali-soluble resin (C) is 5% by weight to 75% by weight, the photopolymerizable compound (D) is 10% by weight to 60% by weight, and the photoinitiator (E) is 1% by weight to 10% by weight.

[0043] The present invention further provides a color filter, which is manufactured by the color filter manufacturing method as described above.

[0044] The present invention further provides a liquid crystal display device, comprising the color filter as described above.

[0045] Based on the above, the present invention provides a method for manufacturing a color filter, which limits the pigment (A) in the photosensitive color resin composition to a compound represented by formula (1) as the pigment (A-1), and limits the post-baking time to 1 minute to 15 minutes under the condition that the post-baking temperature is 200° C. to 250° C., so that the color layer (pattern) in the color filter has a good post-baking residual film rate, thereby being able to produce the color layer (pattern) with a relatively small amount of photosensitive color resin composition, thereby achieving the effect of saving resource use and being environmentally friendly.

[0046] In order to make the above features and advantages of the present invention more clearly understood, embodiments are given below and described in detail as follows. DETAILED DESCRIPTION

[0047] <Color filter and method for manufacturing the same>

[0048] This embodiment provides a color filter, which is manufactured by the following color filter manufacturing method.

[0049] The method for manufacturing a color filter of this embodiment limits the pigment (A) in the photosensitive color resin composition to include a compound represented by formula (1) as the pigment (A-1), and limits the post-baking time to 1 minute to 15 minutes under the condition that the post-baking temperature is 200° C. to 250° C., so that the color layer (pattern) in the color filter has a good post-baking residual film rate, so that the color layer (pattern) can be produced with a relatively small amount of photosensitive color resin composition, thereby achieving the effect of saving resource use and being environmentally friendly.

[0050] The following is a detailed description of the steps (i) to (iv) of the color filter manufacturing method using the lithography process as the main axis:

[0051] Step (i) coating a photosensitive colored resin composition on a substrate to obtain a coating film;

[0052] Step (ii) exposing the coating film to ultraviolet light through a photomask;

[0053] Step (iii) developing the exposed coating film with a developer to obtain a pattern; and

[0054] Step (iv) post-baking the pattern at a temperature range of 200° C. to 250° C. for 1 minute to 15 minutes to obtain a color filter colored layer.

[0055] Process (i)

[0056] The step (i) is to apply the photosensitive colored resin composition on a substrate to obtain a coating film.

[0057] The photosensitive colored resin composition in the step (i) will be described in detail later.

[0058] The substrate in step (i) is not particularly limited, and a transparent substrate may be cited. Specific examples of the transparent substrate include glass substrates having high transmittance to visible light, such as soda-lime glass, low-alkali borosilicate glass, and alkali-free aluminoborosilicate glass; and plastic substrates, such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and polyethylene naphthalate.

[0059] Furthermore, the substrate may be subjected to appropriate pretreatment as required, and the pretreatment may include chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum evaporation, or a combination thereof.

[0060] In addition, in order to drive the panelized liquid crystal to emit light, a transparent electrode made of indium oxide and / or tin oxide can be formed on the surface of the glass substrate or plastic substrate. In addition, when the color filter is applied to a liquid crystal display device, the contrast can be further improved by pre-forming a black matrix. The black matrix can be listed but not limited to a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film dispersed with a light shielding agent.

[0061] The coating method in step (i) is not particularly limited, and examples thereof include coating the photosensitive color resin composition on the substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, or a combination thereof to obtain a coating film.

[0062] After the photosensitive colored resin composition is applied onto the substrate, it may be dried under reduced pressure or pre-baked as necessary to volatilize the solvent.

[0063] The conditions for vacuum drying and pre-baking are not particularly limited and can be adjusted according to the types and proportions of the components. Generally speaking, vacuum drying is performed at a pressure of 0 to 200 mmHg for 1 second to 60 seconds, and pre-baking is performed at a temperature of 70 to 110°C for 1 minute to 15 minutes.

[0064] Step (ii)

[0065] Step (ii) is to expose the coating film with ultraviolet light through a photomask. 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 (ultra) high pressure mercury lamp or a metal halide lamp. The exposure amount of ultraviolet light is not particularly limited, but is preferably 1 to 1000 mJ / cm 2 .

[0066] Process (iii)

[0067] Step (iii) is to develop the exposed coating film with a developer to obtain a pattern.

[0068] The developer used in the development treatment is not particularly limited, and an alkaline developer can be cited. The alkaline developer is not particularly limited, and an aqueous solution of sodium carbonate, sodium hydroxide, etc. can be cited, and an organic base such as dimethylbenzylamine, triethanolamine, etc. can also be used. In addition, a defoamer, a surfactant, or a combination thereof can be added to the developer.

[0069] The method of development treatment is not particularly limited, and examples thereof include a method of dissolving and removing the unexposed portion of the coating film by a shower development method, a spray development method, a dip development method, a puddle development method, and the like.

[0070] Step (iv)

[0071] Step (iv) is to post-bake the pattern at a temperature range of 200° C. to 250° C. for 1 minute to 15 minutes to obtain a colored layer (color filter). It is worth noting that when the post-bake temperature is less than 1 minute or greater than 15 minutes, the post-bake residual film rate of the pattern produced by the photosensitive colored resin composition is poor.

[0072] In addition, the post-bake treatment time is preferably 3 minutes to 10 minutes. When the post-bake treatment time is 3 minutes to 10 minutes and the photosensitive color resin composition contains the pigment (A-1), the pattern produced by the photosensitive color resin composition has a better post-bake residual film rate.

[0073] The heating device for the post-bake treatment is not particularly limited, and examples thereof include heating devices such as a hot plate and an oven.

[0074] On the other hand, the above steps (i) to (iv) do not necessarily need to be performed continuously, and other steps can be inserted into each step as needed. For example, after step (i), a water-soluble resin or an alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is coated on the coating film and dried to increase the sensitivity to ultraviolet light exposure, thereby forming a thin film that prevents oxygen inhibition, and then step (ii) is performed. In addition, after step (iii), the pattern can be further exposed to ultraviolet light to promote the photocrosslinking reaction, and then step (iv) is performed.

[0075] The color filter manufactured by the color filter manufacturing method of this embodiment can be applied to, but not limited to, liquid crystal display devices and the like.

[0076] <Liquid crystal display device and manufacturing method thereof>

[0077] This embodiment provides a liquid crystal display device, which may include a color filter manufactured by the above-mentioned method for manufacturing a color filter.

[0078] When used in a liquid crystal display device, a cover film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, or a combination thereof may be formed on the color filter as needed.

[0079] Specifically, the liquid crystal display component of this embodiment can be manufactured as follows.

[0080] First, two substrates are prepared, and a cover film, a columnar spacer, a transparent conductive film, or a combination thereof is formed on one or both of the substrates. Then, an alignment film is further provided on one or both of the substrates. Then, liquid crystal is injected between the two substrates.

[0081] There is no particular limitation on the liquid crystal display device, and the liquid crystal display device can be applied to, for example, twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS) panels, vertical alignment (VA) panels, and optically compensated birefringence (OCB) panels, etc., which use color filters for coloring in liquid crystal display modes.

[0082] <Photosensitive Colored Resin Composition>

[0083] In this embodiment, the photosensitive colored resin composition includes a pigment (A), an alkali-soluble resin (C), a photopolymerizable compound (D), a photoinitiator (E), and a solvent (F), wherein the pigment (A) includes a pigment (A-1). In addition, if necessary, the photosensitive colored resin composition of this embodiment may selectively include a dye (B), an additive (G), or a combination thereof. The various components of the photosensitive colored resin composition used in this embodiment will be described in detail below:

[0084] 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.

[0085] Pigment (A)

[0086] The pigment (A) may include the pigment (A-1). In addition, the pigment (A) may further include other pigments (A-2) in addition to the pigment (A-1).

[0087] Pigment (A-1)

[0088] The pigment (A-1) is a compound represented by the formula (1).

[0089]

[0090] In formula (1),

[0091] A represents a p-valent organic group, wherein the carbon atom directly bonded to N in the organic group does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, and the carbon chain of the aliphatic hydrocarbon group may contain O, S, and N, and the carbon chain of the aromatic group may contain O, S, and N;

[0092] Bq- It represents the q-valent heteropoly acid anion (heteropoly acid);

[0093] R 1 , R 2 , R 3 , R 4 , and R 5 Each independently represents a hydrogen atom, or a substituted or unsubstituted alkyl group, wherein R 2 , R 3 , R 4 , and R 5 At least one of them is a substituted or unsubstituted alkyl group, R 2 With R 3 Can bond to each other to form a ring structure, R 4 With R 5 Can bond to each other to form a ring structure, multiple R 1 , R 2 , R 3 , R 4 , and R 5 Each may be the same or different;

[0094] R 6 and R 7 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a halogen atom, or a cyano group;

[0095] Ar represents a substituted or unsubstituted divalent aromatic group, and multiple Ars may be the same or different;

[0096] p and q represent integers greater than 2;

[0097] r and s represent an integer greater than 1;

[0098] v represents 0 or 1. When v represents 0, there is no bond;

[0099] t and u each independently represent an integer of 0 to 4;

[0100] t+v and u+v are integers of 0 or more and 4 or less.

[0101] The carbon atom directly bonded to the nitrogen atom (N) by the p-valent organic group represented by A in formula (1) does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, wherein the carbon chain of the aliphatic hydrocarbon group may contain an oxygen atom (O), a sulfur atom (S), and a nitrogen atom (N), and the carbon chain of the aromatic group may also contain O, S, and N. Since the carbon atom directly bonded to N does not have a π bond, the color characteristics such as the hue or transmittance of the cationic color-forming part are not affected by the bonding group A or other color-forming parts, and the same color as the monomer can be maintained.

[0102] In A of formula (1), the aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the terminal directly bonded to N may be any of straight chain, branched or cyclic, as long as the carbon atom at the terminal directly bonded to N does not have a π bond, and the carbon atoms other than the terminal may have an unsaturated bond, and may have a substituent, and the carbon chain of the substituent may contain O, S, and N. The carbon chain of the substituent may contain, for example, a carbonyl group, a carboxyl group, an oxycarbonyl group, an amide group, etc., and the hydrogen atom may be substituted with a halogen atom, etc.

[0103] In addition, in A of formula (1), the aromatic group having the aliphatic hydrocarbon group can be a monocyclic or polycyclic aromatic group having an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, which may have a substituent or may be a heterocyclic ring containing O, S, or N.

[0104] In A of the formula (1), from the viewpoint of the rigidity of the skeleton, A preferably contains a cyclic aliphatic hydrocarbon group or an aromatic group.

[0105] In A of formula (1), from the viewpoint of the firmness of the skeleton, the cyclic aliphatic hydrocarbon group as A is preferably a bridged alicyclic hydrocarbon group. The so-called bridged alicyclic hydrocarbon group refers to a polycyclic aliphatic hydrocarbon group having a cross-linked structure and a polycyclic structure in the aliphatic ring. Examples of the bridged alicyclic hydrocarbon group include norbornane, bicyclo[2.2.2]octane, adamantane, etc. The bridged alicyclic hydrocarbon group is preferably norbornane. In addition, examples of the aromatic group include groups containing a benzene ring or a naphthalene ring, and preferably a group containing a benzene ring. For example, when A is a divalent organic group, examples include a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, or an aromatic group having alkylene groups having 1 to 20 carbon atoms such as xylylene, etc. substituted by two.

[0106] In A of formula (1), the valence p is the number of chromogenic cationic sites constituting the cation, and p represents an integer greater than 2. In this lake pigment, from the viewpoint of heat resistance, the valence p of the cation is preferably greater than 2, and more preferably greater than 3. There is no particular upper limit on p, but from the viewpoint of ease of production, p is preferably less than 4, and more preferably less than 3.

[0107] R 1 , R 2 , R 3 , R 4 , and R 5 Each independently represents a hydrogen atom, or a substituted or unsubstituted alkyl group, wherein R 2 , R 3 , R 4 , and R 5 At least one of is a substituted or unsubstituted alkyl group. 2 , R 3 , R 4 , and R 5 Preferably, each independently represents a substituted or unsubstituted alkyl group. 2 , R 3 , R 4 , and R 5 When each independently represents a substituted or unsubstituted alkyl group, a pattern produced by the photosensitive colored resin composition has a better post-baking residual film rate.

[0108] R 1 , R 2 , R 3 , R 4 , and R 5 The alkyl group in the group is not particularly limited, and examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms, preferably linear or branched alkyl groups having 1 to 8 carbon atoms, more preferably linear or branched alkyl groups having 1 to 5 carbon atoms, and particularly preferably ethyl or methyl groups. There are no particular limitations on the substituents that the alkyl group may have, and examples thereof include halogen atoms, hydroxyl groups, alkoxy groups, and the like.

[0109] From the perspective of chemical stability, R 1 , R 2 , R 3 , R 4 , and R 5 Preferably, each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or R 2 With R 3 Bonded to each other to form a ring structure, R 4 With R 5 They are bonded to each other to form a ring structure, wherein the ring structure may be a pyrrolidine ring, a piperidine ring, or a morpholine ring.

[0110] R1 , R 2 , R 3 , R 4 , and R 5 The above structure can be formed independently, that is, multiple R 1 , R 2 , R 3 , R 4 , and R 5 Each may be the same or different.

[0111] R 6 and R 7 Each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a halogen atom, or a cyano group. 6 and R 7 The substituted or unsubstituted alkyl in the alkyl group is not particularly limited, and is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl groups, and these groups may be linear or branched. There are no particular limitations on the substituents that may be present in the alkyl group, and examples include aryl groups, halogen atoms, hydroxyl groups, alkoxy groups, or combinations thereof.

[0112] Again, R 6 and R 7 The substituted or unsubstituted alkoxy group in the alkoxy group is not particularly limited, and is preferably a linear or branched alkoxy group having 1 to 8 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy groups, wherein these groups may be linear or branched. There are no particular limitations on the substituents that may be present in the alkoxy group, and examples thereof include aryl groups, halogen atoms, hydroxyl groups, and alkoxy groups.

[0113] R 6 and R 7 The halogen atom may include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a combination thereof.

[0114] R 6 and R 7 The number of substitutions, that is, t and u each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1. t+v and u+v are integers of 0 to 4. When t and u are each two or more, the multiple t and u may be the same or different.

[0115] When v represents 0, there is no bond, and the compound represented by formula (1) has a triarylmethane skeleton. 6 and R 7It can be substituted at any position of the triarylmethane skeleton or the aromatic ring having a resonance structure in the skeleton, among which, it is preferably based on -NR 2 R 3 or -NR 4 R 5 The substitution position of the amine group shown is used as a reference and substitution is performed at the meta position.

[0116] The substituted or unsubstituted divalent aromatic group in Ar is not particularly limited, and a plurality of Ars may be the same or different. The aromatic group in Ar may be the same as those listed for the aromatic group in A.

[0117] Ar is preferably a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, and more preferably a substituted or unsubstituted aromatic group containing a condensed polycyclic carbocyclic ring having 10 to 14 carbon atoms. Among them, phenylene or naphthylene is more preferred from the viewpoint of simple structure and low raw material price.

[0118] There are multiple R in one molecule 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 and Ar may be the same or different. 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 The combination of Ar can be adjusted to the desired color.

[0119] Among the compounds represented by formula (1), B q- = represents a q-valent heterogeneous multiple acid anion. The heterogeneous multiple acid anion can be represented by (Y 1 M e O f ) q- In the above ionic formula, M represents a polyatom, Y represents a heteroatom, e represents the composition ratio of the polyatom, and f represents the composition ratio of oxygen atoms. Examples of the polyatom M include molybdenum (Mo), tungsten (W), vanadium (V), titanium (Ti), or niobium (Nb). Examples of the heteroatom Y include silicon (Si), phosphorus (P), arsenic (As), sulfur (S), iron (Fe), and cobalt (Co).

[0120] Among them, B q- The heterogeneous polyacid anion preferably contains at least one of molybdenum (Mo) and tungsten (W), and more preferably contains at least q-valent heterogeneous polyacid anions of tungsten.

[0121] In formula (1), r is the number of cations, and s is the number of anions. r and s are integers greater than 1. When r is greater than 2, the cations in formula (1) can be used alone or in combination. In addition, when s is greater than 2, the anions in formula (1) can be used alone or in combination.

[0122] In formula (1), v represents an integer of 0 or 1. When v represents 0, there is no bond, and the main structure of formula (1) is a triarylmethane skeleton. When v represents 1, the main structure of formula (1) is a xanthene skeleton. Multiple v's may be the same or different. Among the compounds represented by formula (1), it is preferred that the compound contains a triarylmethane skeleton.

[0123] The compound represented by formula (1) can be produced by referring to the specification of International Publication No. 2012 / 144520, for example.

[0124] The above-mentioned pigment (A-1) can be used alone or in combination of two or more.

[0125] Specific examples of the compound represented by formula (1) may include at least one of compounds (1-1) to (1-20). Each of compounds (1-1) to (1-20) contains a cation and a heterogeneous polyacid anion.

[0126] The compound represented by formula (1) is preferably at least one of the compounds represented by compounds (1-1) to (1-4), compounds (1-6) to (1-7), compounds (1-10) to (1-11), compound (1-14), and compound (1-17).

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133] When the photosensitive color resin composition does not contain the pigment (A-1), the post-baking residual film rate of the pattern produced by the photosensitive color resin composition is poor.

[0134] In this embodiment, based on 100 parts by weight of the alkali-soluble resin (C), the pigment (A-1) may be 1 part by weight to 300 parts by weight, preferably 5 parts by weight to 270 parts by weight, and more preferably 10 parts by weight to 250 parts by weight.

[0135] In this embodiment, the pigment (A-1) may be 0.5 to 50 wt%, preferably 1 to 45 wt%, and more preferably 5 to 40 wt%, based on 100 wt% of the total weight of the solid content of the photosensitive colored resin composition.

[0136] Other pigments (A-2)

[0137] In this embodiment, the pigment (A) may further include other pigments (A-2). The other pigments (A-2) may be inorganic pigments, organic pigments, or a combination thereof.

[0138] 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.

[0139] Specific examples of organic pigments include CI Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57:2、58:2、58:4、60:l、63:l、63:2、64:l、81:l、83、88、90:l、97、101、102、104、105、106、108、112、113、114、122、123、144、1 46, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 2 08, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; CI Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38, 39, 40, 50; CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 21, 22, 60, 61, 64, 66; CI Pigment Green 7, 36, 37, 42, 58; CI Pigment Brown 23, 25, 28; CI Pigment Black 1, 7; or a combination thereof.

[0140] The above other pigments (A-2) may be used alone or in combination of two or more.

[0141] The other pigment (A-2) is preferably CI Pigment Blue 15:4, CI Pigment Blue 15:6, or a combination thereof.

[0142] The average particle diameter of the other pigment (A-2) may be 10 nm to 200 nm, preferably 20 nm to 150 nm, and more preferably 30 nm to 130 nm.

[0143] In this embodiment, based on 100 parts by weight of the alkali-soluble resin (C), the other pigment (A-2) may be 0 parts by weight to 299 parts by weight, preferably 0 parts by weight to 265 parts by weight, and more preferably 0 parts by weight to 240 parts by weight.

[0144] In this embodiment, based on 100 parts by weight of the alkali-soluble resin (C), the pigment (A) may be 1 part by weight to 300 parts by weight, preferably 5 parts by weight to 270 parts by weight, and more preferably 10 parts by weight to 250 parts by weight.

[0145] In this embodiment, the pigment (A) may be 0.5 to 50 wt %, preferably 1 to 45 wt %, and more preferably 5 to 40 wt %, based on 100 wt % of the total weight of the solid content of the photosensitive colored resin composition.

[0146] In the photosensitive colored resin composition of the present embodiment, the pigment (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 disperse evenly and finely, the surfactant is preferably a polymer dispersant.

[0147] 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.

[0148] From the viewpoint of being able to preferably disperse the pigment (A) and having good dispersion stability, the polymer dispersant is preferably a polymer dispersant containing a nitrogen atom in the main chain or a side chain and having an amine value.

[0149] Specific examples of the polymer dispersant containing a nitrogen atom in the main chain or the side chain are as follows.

[0150] 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).

[0151] Examples of commercially available products of polyurethanes include Disperbyk 161 (manufactured by BYK-Chemie).

[0152] Examples of commercially available products of unsaturated polyamides include Disperbyk 101 and Disperbyk 130 (manufactured by BYK-Chemie).

[0153] Commercially available products of the polyallylamine derivatives include Ajisper PB821, Ajisper PB822, Ajisper PB824, and Ajisper PB827 (manufactured by Ajinomoto Fine-Techno Co., Ltd.).

[0154] Commercially available products of the polyethyleneimine derivative include Solsperse 33500 (manufactured by Lubrizol Corporation).

[0155] Other commercially available dispersants include Dysperbyk 116, Dysperbyk 140, Dysperbyk 160, Dysperbyk 162, Dysperbyk 163, Dysperbyk 164, Dysperbyk 166, Dysperbyk 167, Dysperbyk 168, Dysperbyk 170, Dysperbyk 171, Dysperbyk 174, Dysperbyk 182, and Dysperbyk 2050 (all manufactured by BYK-Chemie); EFKA 4046 and 4047 (all manufactured by EFKA Chemicals Co.); Solsperse 12000, Solsperse 13250, and Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 24000SC, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 33500, Solsperse 35200, Solsperse 37500 (all manufactured by Lubrizol, Japan); Ajisper PB711, Ajisper 823, Ajisper 880 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), etc.

[0156] The amount of the dispersant used is not particularly limited and can be appropriately adjusted according to needs.

[0157] Dye(B)

[0158] In this embodiment, the photosensitive colored resin composition may optionally include a dye (B). The dye (B) may be a dye (B-1), another dye (B-2), or a combination thereof.

[0159] The dye (B-1) is a compound represented by formula (2).

[0160]

[0161] In formula (2),

[0162] R 8 , R 9 , R 10 , and R 11 Each independently represents a hydrogen atom, -L 1, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L 1 、-OH、-OL 1 、-SO 3 - 、-SO 3 H, -SO 3 M, -COOH, -COOL 1 、-SO 3 L 1 、-SO 2 NHL 2 or -SO 2 NL 2 L 3 A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms;

[0163] R 12 Indicates -SO 3 - 、-SO 3 H, -SO 3 M, -COOH, -COOL 1 、-SO 3 L 1 、-SO 2 NHL 2 or -SO 2 NL 2 L 3 ;

[0164] m represents an integer from 0 to 5; when m represents 2 to 5, multiple R 12 Each may be the same or different;

[0165] X represents a halogen atom;

[0166] n represents 0 or 1;

[0167] L 1 represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted by a halogen atom, wherein -CH 2 - unsubstituted or substituted by -O-, carbonyl or -NL 4 -replace;

[0168] L 4 represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom;

[0169] L 2 and L 3Each independently represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q; wherein the hydrogen atoms in the linear alkyl group having 1 to 10 carbon atoms, the branched alkyl group having 3 to 10 carbon atoms, or the cycloalkyl group having 3 to 30 carbon atoms are unsubstituted or substituted with a substituent selected from the group consisting of a hydroxyl group, a halogen atom, -Q, -CH=CH 2 and -CH=CH-L 1 The group consisting of: -CH in a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 3 to 30 carbon atoms 2 - unsubstituted or substituted by -O-, carbonyl or -NL 4 - replace; or

[0170] L 2 With L 3 bonded to each other to form a heterocyclic group having 1 to 10 carbon atoms, wherein the hydrogen atoms in the heterocyclic group having 1 to 10 carbon atoms are unsubstituted or replaced by L 1 , -OH, or -Q;

[0171] Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, a heteroaromatic group having 5 to 10 carbon atoms, a halogen atom, -L 1 、-OH、-OL 1 、-NO 2 、-CH=CH 2 or -CH=CH-L 1 A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or a substituted halogen atom, -L 1 、-OH、-OL 1 、-NO 2 、-CH=CH 2 or -CH=CH-L 1 a substituted heteroaromatic group having 5 to 10 carbon atoms;

[0172] M represents potassium or sodium.

[0173] In formula (2), L 1 Preferred are, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptane, octyl, cyclooctyl, 2-ethylhexyl, nonyl, decyl, tricyclo[5.3.0.0 3,10 ]Decyl[tricycle(5.3.0.0 3,10 )decanyl], methoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, or epoxypropyl.

[0174] In formula (2), the aromatic hydrocarbon group having 6 to 10 carbon atoms preferably includes, but is not limited to, phenyl or naphthyl.

[0175] In formula (2), -SO 3 L 1 Preferred examples include, but are not limited to, methanesulfonyl, ethanesulfonyl, hexanesulfonyl, or decanesulfonyl.

[0176] In formula (2), -COOL 1 including but not limited to methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, cyclooctyloxycarbonyl, 2-ethylhexyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, tricyclo[5.3.0.0 3,10 ]decylcarbonyl, methoxypropoxycarbonyl, hexyloxypropoxycarbonyl, 2-ethylhexyloxypropoxycarbonyl, or methoxyhexyloxycarbonyl.

[0177] In formula (2), -SO 2 NHL 2 Preferred are sulfamoyl, methylsulfamoyl, ethylsulfamoyl, propylsulfamoyl, isopropylsulfamoyl, butylsulfamoyl, isobutylsulfamoyl, pentylsulfamoyl, isopentylsulfamoyl, neopentylsulfamoyl, cyclopentylsulfamoyl, hexylsulfamoyl, cyclohexylsulfamoyl, heptylsulfamoyl, cycloheptylsulfamoyl, octylsulfamoyl, cyclooctylsulfamoyl, 2-ethylhexylsulfamoyl, nonylsulfamoyl, decylsulfamoyl, tricyclo[5.3.0.0 3,10 ]Decylsulfamoyl, methoxypropylsulfamoyl, hexyloxypropylsulfamoyl, 2-ethylhexyloxypropylsulfamoyl, methoxyhexylsulfamoyl, epoxypropylsulfamoyl, 1,5-dimethylhexylsulfamoyl, propoxypropylsulfamoyl, isopropoxypropylsulfamoyl, 3-phenyl-1-methylpropylsulfamoyl,

[0178]

[0179]

[0180]

[0181] (Ra represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted by a halogen atom, or an alkoxy group having 1 to 3 carbon atoms substituted by a halogen atom),

[0182]

[0183]

[0184] (R b represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted by a halogen atom, or an alkoxy group having 1 to 3 carbon atoms substituted by a halogen atom),

[0185]

[0186]

[0187] The dye (B-1) includes, but is not limited to, a compound represented by formula (2-1), a compound represented by formula (2-2), a compound represented by formula (2-3), a compound represented by formula (2-4), or a combination thereof.

[0188]

[0189] In formula (2-1),

[0190] R 13 , R 14 , R 15 , and R 16 Each independently represents a hydrogen atom, -L 1 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L 1 、-OH、-OL 1 、-SO 3 - 、-SO 3 H, -SO 3 Na, -COOH, -COOL 1 、-SO 3 L 1 、-SO 2 NHL 2 or -SO 2 NL 2 L 3 A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms;

[0191] R 17 Represents hydrogen atom, -SO 3 - 、-SO 3 H, -SO 2 NHL2 or -SO 2 NL 2 L 3 ;

[0192] R 18 Indicates -SO 3 - 、-SO 3 H, -SO 2 NHL 2 or -SO 2 NL 2 L 3 ;

[0193] X represents a halogen atom;

[0194] n represents 0 or 1.

[0195]

[0196] In formula (2-2),

[0197] R 19 , R 20 , R 21 , and R 22 Each independently represents a hydrogen atom, -L 5 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L 5 、-OH、-OL 5 、-SO 3 - 、-SO 3 H, -SO 3 Na, -COOH, -COOL 5 、-SO 3 L 5 , or -SO 2 NHL 7 A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms;

[0198] R 23 Indicates -SO 3 - 、-SO 3 Na, -COOH, -COOL 5 、-SO 3 H, or -SO 2 NHL 7 ;

[0199] u 1 represents an integer from 0 to 5. 1 Indicates 2 to 5, multiple u 1 Each may be the same or different;

[0200] X represents a halogen atom;

[0201] n represents 0 or 1;

[0202] L 5 represents an alkyl group having 1 to 10 carbon atoms, or a halogen atom or -OL 6 A substituted alkyl group having 1 to 10 carbon atoms;

[0203] L 6 represents an alkyl group having 1 to 10 carbon atoms; and

[0204] L 7 Represents a hydrogen atom, -L 5 、-COOL 5 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or -L 5 or -OL 5 A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms.

[0205]

[0206] In formula (2-3),

[0207] R 24 and R 25 Each independently represents a phenyl group, or a halogen atom, -L 5 , -OL 5 、-COOL 5 、-SO 3 L 5 , or -SO 2 NHL 7 Substituted phenyl;

[0208] R 26 Indicates -SO 3 - , or -SO 2 NHL 7 ;

[0209] R 27 Represents hydrogen atom, -SO 3 - , or -SO 2 NHL 7 ;

[0210] X represents a halogen atom;

[0211] n represents 0 or 1;

[0212] L 5 represents an alkyl group having 1 to 10 carbon atoms, or a halogen atom or -OL 6 A substituted alkyl group having 1 to 10 carbon atoms;

[0213] L6 represents an alkyl group having 1 to 10 carbon atoms; and

[0214] L 7 Represents a hydrogen atom, -L 5 、-COOL 5 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or -L 5 or -OL 5 A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms.

[0215]

[0216] In formula (2-4),

[0217] R 28 and R 29 Each independently represents a phenyl group, or a halogen atom, -L 5 , or -SO 2 NHL 7 Substituted phenyl;

[0218] R 30 Indicates -SO 3 - , or -SO 2 NHL 7 ;

[0219] X represents a halogen atom;

[0220] n represents 0 or 1;

[0221] L 5 represents an alkyl group having 1 to 10 carbon atoms, or a halogen atom or -OL 6 A substituted alkyl group having 1 to 10 carbon atoms;

[0222] L 6 represents an alkyl group having 1 to 10 carbon atoms; and

[0223] L 7 Represents a hydrogen atom, -L 5 、-COOL 5 , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or -L 5 or -OL 5 A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms.

[0224] The above dye (B-1) can be generally used alone or in combination of two or more.

[0225] Specific compounds of the dye (B-1) include, but are not limited to, compounds represented by formula (i-1) to formula (i-31), or a combination thereof.

[0226]

[0227] In formula (i-1),

[0228] R c and R d Each independently represents a hydrogen atom, -SO 3 - , -COOH, or -SO 2 NHL 8 ; L 8 represents 2-ethylhexyl;

[0229] X represents a halogen atom;

[0230] n represents 0 or 1.

[0231]

[0232] In formula (i-2),

[0233] R e Represents hydrogen atom, -SO 3 - , -COOH, or -SO 2 NHL 8 ;

[0234] L 8 represents 2-ethylhexyl;

[0235] X represents a halogen atom;

[0236] n represents 0 or 1.

[0237]

[0238] In formula (i-3),

[0239] R e Represents hydrogen atom, -SO 3 - , -COOH, or -SO 2 NHL 8 ;

[0240] L 8 represents 2-ethylhexyl;

[0241] X represents a halogen atom;

[0242] n represents 0 or 1.

[0243]

[0244] In formula (i-4),

[0245] R f , R g and R hEach independently represents 3 - 、-SO 3 Na, or -SO 2 NHL 8 ;

[0246] L 8 It represents 2-ethylhexyl.

[0247]

[0248] In formula (i-5),

[0249] R f , R g and R h Each independently represents 3 - 、-SO 3 Na, or -SO 2 NHL 8 ;

[0250] L 8 It represents 2-ethylhexyl.

[0251]

[0252] In formula (i-6),

[0253] R i , R j and R k Each independently represents a hydrogen atom, -SO 3 - 、-SO 3 H, or -SO 2 NHL 8 ; L 8 It represents 2-ethylhexyl.

[0254]

[0255] In formula (i-7),

[0256] R i , R j and R k Each independently represents a hydrogen atom, -SO 3 - 、-SO 3 H, or -SO 2 NHL 8 ; L 8 It represents 2-ethylhexyl.

[0257]

[0258] In formula (i-8),

[0259] R l , R m and R n Each independently represents 3 - 、-SO 3 Na, or -SO 2 NHL 8 ;

[0260] L 8 It represents 2-ethylhexyl.

[0261]

[0262] In formula (i-9),

[0263] R l , R m and R n Each independently represents 3 - 、-SO 3 Na, or -SO 2 NHL 8 ;

[0264] L 8 It represents 2-ethylhexyl.

[0265]

[0266] In formula (i-10),

[0267] R p , R q and R r Each independently represents a hydrogen atom, -SO 3 - 、-SO 3 H, or -SO 2 NHL 8 ; L 8 It represents 2-ethylhexyl.

[0268]

[0269] In formula (i-11),

[0270] R p , R q and R r Each independently represents a hydrogen atom, -SO 3 - 、-SO 3 H, or -SO 2 NHL 8 ; L8 It represents 2-ethylhexyl.

[0271]

[0272]

[0273]

[0274]

[0275]

[0276] The above dyes (B-1) may be used alone or in combination of two or more.

[0277] Specific examples of the dye (B-1) of this embodiment preferably include the formula (i-1) (R c and R d For-SO 3 -, a is 0) [CI acid red dye 52], formula (i-22) [CI acid red dye 289], a dye represented by formula (i-28), a dye represented by formula (i-31), or a combination thereof.

[0278] When the photosensitive colored resin composition further includes the dye (B-1), the pattern produced by the photosensitive colored resin composition has a better post-baking residual film rate.

[0279] In this embodiment, based on 100 parts by weight of the alkali-soluble resin (C), the dye (B-1) may be 1 to 90 parts by weight, preferably 3 to 80 parts by weight, and more preferably 5 to 70 parts by weight.

[0280] In this embodiment, the dye (B-1) may be 0.1 to 20 wt %, preferably 0.5 to 18 wt %, and more preferably 1 to 15 wt %, based on 100 wt % of the total weight of the solid content of the photosensitive colored resin composition.

[0281] Other dyes(B-2)

[0282] When the photosensitive colored resin composition may further include other dyes (B-2) in addition to the dye (B-1), the other dyes (B-2) include but are not limited to azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, or combinations thereof.

[0283] Azo dyes include, but are not limited to, CI Acid Yellow 11, Acid Orange 7, Acid Red 37, Acid Red 180, Acid Blue 29, Direct Red 28, Direct Red 83, Direct Yellow 12, Direct Orange 26, Direct Green 28, Direct Green 59, Reactive Yellow 2, Reactive Red 17, Reactive Red 120, Reactive Black 5, Disperse Orange 5, Disperse Red 58, Disperse Blue 165, Basic Blue 41, Basic Red 18, Mordant Red 7, Mordant Yellow 5, Mordant Black 7, or combinations thereof.

[0284] Anthraquinone dyes include, but are not limited to, CI Bader Blue 4, Acid Blue 40, Acid Green 25, Reactive Blue 19, Reactive Blue 49, Disperse Red 60, Disperse Blue 56, Disperse Blue 60, or combinations thereof.

[0285] Phthalocyanine dyes include but are not limited to CI Basic Blue 5 and the like.

[0286] The quinoneimine dyes include, but are not limited to, CI Basic Blue 3, CI Basic Blue 9, or a combination thereof.

[0287] The quinoline dye is CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, or a combination thereof.

[0288] Nitro dyes include, but are not limited to, CI Acid Yellow 1, Acid Orange 3, Disperse Yellow 42, or a combination thereof.

[0289] The above other dyes (B-2) may be used alone or in combination of two or more.

[0290] The other dye (B-2) preferably includes CI Acid Red 37, CI Acid Blue 29, or a combination thereof.

[0291] In this embodiment, based on 100 parts by weight of the alkali-soluble resin (C), the other dye (B-2) may be 0 parts by weight to 89 parts by weight, preferably 0 parts by weight to 77 parts by weight, and more preferably 0 parts by weight to 65 parts by weight.

[0292] In this embodiment, based on 100 parts by weight of the alkali-soluble resin (C), the dye (B) may be 1 to 90 parts by weight, preferably 3 to 80 parts by weight, and more preferably 5 to 70 parts by weight.

[0293] In this embodiment, the dye (B) may be 0.1 to 20 wt %, preferably 0.5 to 18 wt %, and more preferably 1 to 15 wt %, based on 100 wt % of the total solid content of the photosensitive colored resin composition.

[0294] Alkali soluble resin (C)

[0295] The alkali-soluble resin (C) of this embodiment may include a first alkali-soluble resin (C-1). In addition, the alkali-soluble resin (C) of this embodiment may further include a second alkali-soluble resin (C-2).

[0296] First alkali-soluble resin (C-1)

[0297] The first alkali-soluble resin (C-1) of this embodiment is obtained by copolymerizing a carboxylic acid group-containing ethylenically unsaturated monomer (c-1-1) with other copolymerizable ethylenically unsaturated monomers (c-1-2).

[0298] The ethylenically unsaturated monomers containing carboxylic acid groups (c-1-1) can 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.

[0299] In this embodiment, the usage amount of the carboxylic acid group-containing ethylenically unsaturated monomer (c-1-1) and other copolymerizable ethylenically unsaturated monomers (c-1-2) based on the first alkali-soluble resin (C-1) is 100 parts by weight, and the usage amount of the carboxylic acid group-containing ethylenically unsaturated monomer (c-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.

[0300] Other copolymerizable ethylenically unsaturated monomers (c-1-2) can be used alone or in combination, and other copolymerizable ethylenically unsaturated monomers (c-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, 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, dicyclopentenyloxyethyl acrylate (DCPOA), etc.; acrylate-nitrogen, nitrogen-dimethylaminoethyl ester, methacrylate-nitrogen, nitrogen-dimethylaminoethyl ester, acrylate-nitrogen, nitrogen-diethylaminopropyl ester, methacrylate-nitrogen, nitrogen-dimethylaminopropyl ester, acrylate-nitrogen, nitrogen-dibutylaminopropyl ester, nitrogen-methacrylate iso-butylaminoethyl ester; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, etc.;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. ;

[0301] Other copolymerizable ethylenically unsaturated monomers (c-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.

[0302] In this embodiment, the amount of the carboxylic acid group-containing ethylenically unsaturated monomer (c-1-1) and other copolymerizable ethylenically unsaturated monomers (c-1-2) based on the first alkali-soluble resin (C-1) is 100 parts by weight, and the amount of other copolymerizable ethylenically unsaturated monomers (c-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.

[0303] There is no particular limitation on the preparation method of the first alkali-soluble resin (C-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.

[0304] 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.

[0305] The first alkali-soluble resin (C-1) may be used alone or in combination of two or more.

[0306] The first alkali-soluble resin (C-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 colloid permeation chromatography (GPC).

[0307] In this embodiment, based on 100 parts by weight of the alkali-soluble resin (C), the first alkali-soluble resin (C-1) is used in an amount of 10 to 100 parts by weight, preferably 20 to 90 parts by weight, and more preferably 30 to 80 parts by weight.

[0308] Second alkali-soluble resin (C-2)

[0309] The second alkali-soluble resin (C-2) of this embodiment is prepared by polymerization of a mixture, and the mixture includes an epoxy compound (c-2-1) having at least two epoxy groups and a compound (c-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. In addition, the mixture may further selectively include a carboxylic anhydride compound (c-2-3) and / or an epoxy-containing compound (c-2-4).

[0310] The epoxy compound (c-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 (c-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 (c-2-1). Specifically, the epoxy compound (c-2-1) having at least two epoxy groups, for example, has a structure as shown in the following formula (3-1):

[0311]

[0312] In formula (3-1),

[0313] R 1c、 R 2c、 R 3c and R 4c Each of R1c, R2c, R3c, R4c, R5c, R6c, R7c, R8c, R9c, R10c, R11c, R12c, R13c, R14c, R15c, R16c, R17c, R18c, R19c, R20c, R21c, R22c, R23c, R24c, R25c, R26c, R27c 2c、 R 3c and R 4c Each may be the same or different.

[0314] The epoxy compound (c-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.

[0315] 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.

[0316] 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.

[0317] 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.

[0318] Secondly, the epoxy compound (c-2-1) having at least two epoxy groups may also have a structure as shown in the following formula (3-2):

[0319]

[0320] 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;

[0321] g represents an integer from 0 to 10.

[0322] The epoxy compound (c-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.

[0323]

[0324] 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.

[0325] Furthermore, the epoxy compound (c-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 dehydrohalogenation is performed by adding an excess of halogenated propylene oxide to obtain the epoxy compound (c-2-1) having at least two epoxy groups as shown in formula (3-2).

[0326]

[0327] 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;

[0328] 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.

[0329] 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.

[0330] 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.

[0331] 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.

[0332] Specific examples of the acid catalyst include, but are not limited to, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride, etc., among which p-toluenesulfonic acid, sulfuric acid or hydrochloric acid is preferred. The acid catalysts can be used alone or in combination.

[0333] 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%.

[0334] 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.

[0335] 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.

[0336] 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).

[0337] 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.

[0338] 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 to separate and remove water, and halogenated propylene oxide may be continuously refluxed into the reaction system.

[0339] 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.

[0340] 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.

[0341] 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.

[0342] 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.

[0343] 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.

[0344] 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 (c-2-1) having at least two epoxy groups as shown in formula (3-2). The epoxy compound (c-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.

[0345] The compound (c-2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is, for example, selected from the group consisting of (1) to (3) 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 (c-2-3) contained in the mixture of the second alkali-soluble resin (C-2) described below, and thus will not be described in detail herein.

[0346] The mixture of the second alkali-soluble resin (C-2) may further selectively contain a carboxylic anhydride compound (c-2-3) and / or an epoxy group-containing compound (c-2-4). The carboxylic anhydride compound (c-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.

[0347] The epoxy group-containing compound (c-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.).

[0348] The second alkali-soluble resin (C-2) can be obtained by polymerization reaction of an epoxy compound (c-2-1) having at least two epoxy groups of formula (3-1) and a compound (c-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 (c-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 (c-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 (c-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 (c-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.

[0349] The second alkali-soluble resin (C-2) can be obtained by reacting an epoxy compound (c-2-1) having at least two epoxy groups of formula (3-2) with a compound (c-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 (c-2-3) and / or an epoxy-containing compound (c-2-4) for polymerization. The total equivalent of epoxy groups on the epoxy compound (c-2-1) having at least two epoxy groups of formula (3-2) is 1 equivalent, and the acid value equivalent of the compound (c-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 (c-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 %.

[0350] When preparing the second alkali-soluble resin (C-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 (c-2-1) having at least two epoxy groups and the compound (c-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.

[0351] 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, etc. In general, the above-mentioned polymerization inhibitors can be used alone or in combination. Based on the total amount of the epoxy compound having at least two epoxy groups (c-2-1) and the compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (c-2-2) 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.

[0352] When preparing the second alkali-soluble resin (C-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 (C-2) is preferably 50 mgKOH / g to 200 mgKOH / g, and more preferably 60 mgKOH / g to 150 mgKOH / g.

[0353] The second alkali-soluble resin (C-2) has a polystyrene-equivalent number average molecular weight of 500 to 10,000, preferably 800 to 8,000, and more preferably 1,000 to 6,000, as measured by colloid permeation chromatography.

[0354] The second alkali-soluble resin (C-2) may be used alone or in combination of two or more.

[0355] In this embodiment, based on 100 parts by weight of the alkali-soluble resin (C), the amount of the second alkali-soluble resin (C-2) is 0 to 90 parts by weight, preferably 10 to 80 parts by weight, and more preferably 20 to 70 parts by weight.

[0356] In this embodiment, the alkali-soluble resin (C) may be 5 to 75 wt %, preferably 8 to 70 wt %, and more preferably 10 to 65 wt %, based on 100 wt % of the total weight of the solid content of the photosensitive coloring resin composition.

[0357] Photopolymerizable compound (D)

[0358] The photopolymerizable compound (D) 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.

[0359] 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.

[0360] 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. ,

[0361] Specific examples of the photopolymerizable compound (D) 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.

[0362] Specific examples of the photopolymerizable compound (D) are more preferably dipentaerythritol hexaacrylate, dipentaerythritol tetraacrylate, EO-modified trimethylolpropyl trimethacrylate, or a combination thereof.

[0363] The photopolymerizable compound (D) may be used alone or in combination of two or more.

[0364] The photopolymerizable compound (D) may be contained in an amount of 30 to 450 parts by weight, preferably 35 to 400 parts by weight, and more preferably 40 to 350 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C).

[0365] In this embodiment, the photopolymerizable compound (D) may be 10 to 60 wt %, preferably 13 to 55 wt %, and more preferably 15 to 50 wt %, based on 100 wt % of the total solid content of the photosensitive colored resin composition.

[0366] Photoinitiator (E)

[0367] The photoinitiator (E) of this embodiment may be a free radical photoinitiator.

[0368] Examples of the photoinitiator (E) include acetophenone compounds, biimidazole compounds, acyl oxime compounds, or combinations thereof.

[0369] 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-methylthio phenyl)-2-morpholino-1-propanone, 2-benzyl-2-N,N-di-methylamino-1-(4-morpholinophenyl)-1-butanone, or a combination thereof.

[0370] 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.

[0371] The acyl oxime compound is selected from ethane ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), such as CGI-242 manufactured by Ciba Specialty Chemicals, whose structure is shown in the following formula (4-1), 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime), such as Ciba Specialty Chemicals, which has a structure shown in the following formula (4-1), and 1-[4-(benzoyl)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime). 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-acetyl oxime) (Ethanone, 1-[9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), such as that manufactured by Asahi Denka Co., Ltd., whose structure is shown in the following formula (4-3)), or a combination thereof.

[0372]

[0373]

[0374] In one embodiment, the photoinitiator (E) 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 most preferred.

[0375] Preferred photoinitiators (E) include 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime) (e.g., a product called CGI-124 manufactured by Ciba Specialty Chemicals), 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 4,4'-bis(diethylamino)benzophenone, or a combination thereof.

[0376] The above-mentioned photoinitiators (E) may be used alone or in combination of two or more.

[0377] The photoinitiator (E) may be present in an amount of 2 to 20 parts by weight, preferably 2 to 15 parts by weight, and more preferably 2 to 10 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C).

[0378] In this embodiment, the photoinitiator (E) may be 1 to 10 wt %, preferably 1 to 8 wt %, and more preferably 1 to 5 wt %, based on 100 wt % of the total weight of the solid content of the photosensitive colored resin composition.

[0379] Solvent (F)

[0380] The preparation of the photosensitive colored resin composition of this embodiment is usually to first dissolve the components other than the pigment (A) in a solvent (F) to prepare a liquid composition, and then add the pigment (A) and mix evenly. The solvent (F) needs to be selected to dissolve the alkali-soluble resin (C), the photopolymerizable compound (D), and the photoinitiator (E), and needs to be non-reactive with these components and have appropriate volatility. In addition, when adding the dye (B) and / or the additive (G), the solvent (F) needs to be selected to dissolve the dye (B) and / or the additive (G), and needs to be non-reactive with these components and have appropriate volatility.

[0381] In addition, the solvent (F) may be the same as the solvent used to prepare the alkali-soluble resin (C), which will not be described in detail. The solvent may be used alone or in combination. The solvent (F) preferably includes propylene glycol methyl ether acetate, cyclohexanone, 3-ethoxyethyl propionate, or a combination thereof.

[0382] The solvent (F) may be 500 to 5000 parts by weight, preferably 800 to 4500 parts by weight, and more preferably 1000 to 4000 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C).

[0383] Additives (G)

[0384] In this embodiment, the photosensitive colored resin composition further includes additives (G), such as fillers, polymer compounds other than the alkali-soluble resin (C), adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents, and the like.

[0385] Examples of fillers include glass, aluminum, or a combination thereof.

[0386] Examples of the polymer compound include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and combinations thereof.

[0387] 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.

[0388] Examples of the antioxidant include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, or a combination thereof.

[0389] Examples of the ultraviolet absorber include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenylazide, alkoxyphenone, or a combination thereof.

[0390] As the anti-agglomeration agent, sodium polyacrylate can be mentioned.

[0391] The above-mentioned additives (G) may be used alone or in combination.

[0392] The additive (G) is preferably 3-thiolpropyltrimethoxysilane, 2,2-thiobis(4-methyl-6-tert-butylphenol), or a combination thereof.

[0393] The additive (G) may be included in an amount of 0.1 to 10 parts by weight, preferably 0.3 to 7 parts by weight, and more preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C).

[0394] <Method for preparing photosensitive colored resin composition>

[0395] 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 pigment (A) is added to a solvent (F) to prepare a pigment dispersion, and then an alkali-soluble resin (C), a photopolymerizable compound (D), a photoinitiator (E), and an additive (G) used as needed are added to the pigment dispersion and mixed; (2) A method in which a pigment (A), an alkali-soluble resin (C), a photopolymerizable compound (D), a photoinitiator (E), and an additive (G) used as needed are added to a solvent (F) at the same time and mixed; (3) A method in which an alkali-soluble resin (C), a photopolymerizable compound (D), a photoinitiator (E), and an additive (G) used as needed are first added to a solvent (F) and mixed, and then a pigment (A) is added and dispersed; and (4) a method in which a pigment (A) and a portion of an alkali-soluble resin (C) are first added to a solvent (F) to prepare a pigment dispersion, and then another portion of an alkali-soluble resin (C), a photopolymerizable compound (D), a photoinitiator (E), and an additive (G) used as needed are added to the pigment dispersion and mixed, etc.

[0396] It should be noted that in the above examples, a method for dispersing the pigment (A) is listed. When a dye (B) is used, since the dye (B) has a high solvent solubility, a preparation process of pre-dissolving the dye (B) in the solvent (F) can be adopted; or a preparation process of dissolving the dye (B) and other components in the solvent (F) at the same time can be adopted.

[0397] 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.

[0398] 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, vibrating ball mills, paint conditioners, continuous disc type bead mills, continuous ring type bead mills, and other bead mills. 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.

[0399] The present invention will be further described with reference to the following examples. However, it should be understood that these examples are only for illustration and should not be construed as limitations of the present invention.

[0400] Synthesis Example of Alkali-Soluble Resin (C)

[0401] Synthesis Example C-1-1

[0402] 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 C-1-1.

[0403] Synthesis Example C-1-2

[0404] 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 C-1-2.

[0405] Synthesis Example C-1-3

[0406] 2 parts by weight of 2,2'-azobisisobutyronitrile, 300 parts by weight of dipropylene glycol methyl ether, 20 parts by weight of 2-methacryloylethoxysuccinate, 15 parts by weight of dicyclopentenyloxyethyl acrylate and 65 parts by weight of benzyl methacrylate were placed in a round-bottom flask equipped with a stirrer and a condenser, and the inside 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 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 C-1-3.

[0407] Examples 1 to 11 and Comparative Examples 1 to 4

[0408] Examples 1 to 11 and Comparative Examples 1 to 4 of the photosensitive colored resin composition are described below:

[0409] Example 1

[0410] a. Preparation of photosensitive colored resin composition

[0411] First, 1.0 parts by weight of the pigment (A-1-1) (i.e., compound (1-1)), 0.6 parts by weight of Ajisper PB821 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) (as a dispersant), 8.4 parts by weight of propylene glycol methyl ether acetate (PGMEA, manufactured by Daicel-Allnex Co., Ltd.), and 2.0 parts by weight of zirconia beads having 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 having a particle size of 0.1 mm were added, and the mixture was shaken for 20 hours using a paint shaker to obtain a pigment dispersion of Example 1.

[0412] Next, 10 parts by weight of the above-mentioned pigment dispersion (containing 1.0 parts by weight of the pigment (A-1-1)), 100 parts by weight of the alkali-soluble resin of Synthesis Example C-1-1 (hereinafter referred to as C-1-1), 30 parts by weight of dipentaerythritol hexaacrylate (hereinafter referred to as D-1), and 2 parts by weight of 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime) (trade name OXE-01, manufactured by BASF) (hereinafter referred to as E-1) were added to a mixed solvent of 451.6 parts by weight of propylene glycol methyl ether acetate (hereinafter referred to as F-1) and 40 parts by weight of ethyl 3-ethoxypropionate (hereinafter referred to as F-2), and the mixture was stirred uniformly with a shaking type stirrer to obtain the photosensitive coloring resin composition of Example 1.

[0413] b. Fabrication of patterns (which can be used as coloring layers of color filters)

[0414] The photosensitive colored resin composition of Example 1 was applied on a 100 mm×100 mm glass substrate by spin coating, and then dried under reduced pressure at a pressure of 100 mmHg for 30 seconds, and then pre-baked at a temperature of 90°C for 2 minutes to form a pre-baked coating film with a thickness of 1.2 μm. The pre-baked coating film was then exposed to ultraviolet light (exposure machine Canon PLA-501F) at 100 mJ / cm 2 After the pre-baked coating film is irradiated with a light amount of , it is immersed in a developer at 23°C for 1 minute, washed with pure water, and then post-baked at 200°C for 1 minute to form a pattern with a film thickness of 1.0 μm (which can be used as a coloring layer of a color filter) on the glass substrate.

[0415] The obtained pattern of Example 1 was evaluated by the evaluation method described below. The results are shown in Table 1.

[0416] Examples 2 to 11, Comparative Examples 1 to 4

[0417] The preparation of the photosensitive colored resin composition and the colored layer (color filter) of Examples 2 to 21 and Comparative Examples 1 to 4 was prepared by the same process as that of Example 1, and the difference was that the types of components and the amounts used of the photosensitive colored resin composition and the temperature and time of the post-baking treatment were changed. Among them, Examples 2 to 21 are shown in Table 1, and Comparative Examples 1 to 4 are shown in Table 2). The components corresponding to the numbers in Table 1 and Table 2 are shown in Table 3. The prepared photosensitive colored resin composition was evaluated in the evaluation method described below, and the results of Examples 2 to 21 and Comparative Examples 1 to 4 are shown in Table 1 and Table 2, respectively.

[0418] [Table 1]

[0419]

[0420] [Table 1 (continued)]

[0421]

[0422] [Table 2]

[0423]

[0424] [Table 3]

[0425]

[0426]

[0427] [Evaluation method]

[0428] Post-baking residual film rate

[0429] The film thickness of the formed pattern was measured before and after post-baking using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Technology Co., Ltd.), and the post-baking residual film ratio was calculated according to the following formula.

[0430] Post-baking residual film rate (%) = (film thickness after post-baking / film thickness before post-baking) × 100 (%)

[0431] A larger value indicates that the residual film rate after post-baking is high and good. If the residual film rate is high, it is less likely to cause unfavorable conditions such as cracks or haze due to film shrinkage during heating.

[0432] ※: Post-baking residual film rate>98%.

[0433] ◎: 98%≧Post-baking residual film rate>95%.

[0434] ○: 95% ≧ Post-baking residual film rate > 93%.

[0435] △: 93% ≧ Post-baking residual film rate > 90%.

[0436] ╳: Post-baking residual film rate ≤ 90%.

[0437] <Evaluation Results>

[0438] As can be seen from Tables 1 and 2, the post-baking time is not 1 minute to 15 minutes and / or the photosensitive color resin composition does not contain the pigment (A-1) The color layer produced (Comparative Examples 1 to 4), under the condition of the post-baking temperature of 200 ° C to 250 ° C, the post-baking time is 1 minute to 15 minutes and the photosensitive color resin composition contains the pigment (A-1) (Examples 1 to 21), the pattern (color layer) produced by the photosensitive color resin composition has a good post-baking residual film rate.

[0439] Among them, when the post-baking time is greater than 15 minutes (Comparative Examples 3 and 4), the post-baking residual film rate of the pattern produced by the photosensitive colored resin composition is not good.

[0440] In addition, when the photosensitive color resin composition did not contain the pigment (A-1) (Comparative Examples 1 and 2), the post-baking residual film rate of the pattern produced by the photosensitive color resin composition was poor.

[0441] When the photosensitive colored resin composition contains the pigment (A-1) corresponding to R in the formula (1) 2 , R 3 , R 4 , and R 5 When each independently represents a substituted or unsubstituted alkyl group, a pattern produced by the photosensitive colored resin composition has a better post-baking residual film rate.

[0442] When the post-baking time is between 3 minutes and 10 minutes and the photosensitive colored resin composition contains the pigment (A-1), the pattern produced has a better post-baking residual film rate.

[0443] When the photosensitive colored resin composition further includes the dye (B-1), the pattern produced by the photosensitive colored resin composition has a better post-baking residual film rate.

[0444] In summary, the present invention provides a method for manufacturing a color filter, wherein the photosensitive colored resin composition used includes a compound represented by formula (1) as a pigment (A-1) and the pattern is post-baked for 1 minute to 15 minutes at a post-baking temperature of 200° C. to 250° C., so that the color layer (pattern) in the color filter has a good post-baking residual film rate, thereby avoiding problems such as color mixing and pattern dissolution; at the same time, the color layer (pattern) can be prepared with a relatively small amount of photosensitive colored resin composition, thereby achieving the effect of saving resources and being environmentally friendly.

[0445] 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 method for manufacturing a color filter, It is characterized in that include: Applying a photosensitive colored resin composition on a substrate to obtain a coating film; exposing the coating film through a photomask; Performing a developing process on the exposed coating film with a developer to obtain a pattern; as well as The pattern is post-baked at a temperature range of 200° C. to 250° C. for 1 minute to 15 minutes. The photosensitive colored resin composition comprises a pigment (A), an alkali-soluble resin (C), a photopolymerizable compound (D), a photoinitiator (E), and a solvent (F), The pigment (A) includes a pigment (A-1), wherein the pigment (A-1) is a compound represented by formula (1), In formula (1), A represents a p-valent organic group, wherein the carbon atom directly bonded to N in the organic group does not have a π bond, and the organic group represents an aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at least at the end directly bonded to N, or an aromatic group having the aliphatic hydrocarbon group, the carbon chain of the aliphatic hydrocarbon group may contain O, S, and N, and the carbon chain of the aromatic group may contain O, S, and N; B q- It represents the q-valent heterogeneous polyacid anion; R 1 , R 2 , R 3 , R 4 , and R 5 Each independently represents a hydrogen atom, or a substituted or unsubstituted alkyl group, wherein R 2 , R 3 , R 4 , and R 5 At least one of them is a substituted or unsubstituted alkyl group, R 2 With R 3 Can bond to each other to form a ring structure, R 4 With R 5 Can bond to each other to form a ring structure, multiple R 1 , R 2 , R 3 , R 4 , and R 5 Each may be the same or different; R 6 and R 7 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a halogen atom, or a cyano group; Ar represents a substituted or unsubstituted divalent aromatic group, and multiple Ars may be the same or different; p and q represent integers greater than 2; r and s represent an integer greater than 1; v represents 0 or 1. When v represents 0, there is no bond; t and u each independently represent an integer of 0 to 4; t+v and u+v are integers of 0 or more and 4 or less.

2. The method for manufacturing a color filter according to claim 1, It is characterized in that R 2 , R 3 , R 4 , and R 5 Each independently represents a substituted or unsubstituted alkyl group.

3. The method for manufacturing a color filter according to claim 1, It is characterized in that B q- In the embodiment, the heterogeneous multiple acid anions contain at least one of molybdenum and tungsten.

4. The method for manufacturing a color filter according to claim 1, It is characterized in that The post-baking treatment takes 3 to 10 minutes.

5. The method for manufacturing a color filter according to claim 1, It is characterized in that The photosensitive colored resin composition further includes a dye (B), wherein the dye (B) includes a dye (B-1), wherein the dye (B-1) is a compound represented by formula (2), In formula (2), R 8 、R 9 、R 10 、and R 11 each independently represents a hydrogen atom, -L 1 、an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms substituted by a halogen atom, -L 1 、-OH, -OL 1 、-SO 3 - 、-SO 3 H, -SO 3 M, -COOH, -COOL 1 、-SO 3 L 1 、-SO 2 NHL 2 or -SO 2 NL 2 L 3 substituted aromatic hydrocarbon group having 6 to 10 carbon atoms; R 12 represents -SO 3 - 、-SO 3 H、-SO 3 M、-COOH、-COOL 1 、-SO 3 L 1 、-SO 2 NHL 2 or -SO 2 NL 2 L 3 ; m represents an integer from 0 to 5; when m represents 2 to 5, multiple R 12 Each may be the same or different; X represents a halogen atom; n represents 0 or 1; L 1 represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted by a halogen atom, wherein -CH 2 - unsubstituted or substituted by -O-, carbonyl or -NL 4 -replace; L 4 represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom; L 2 and L 3 Each independently represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q; wherein the hydrogen atoms in the linear alkyl group having 1 to 10 carbon atoms, the branched alkyl group having 3 to 10 carbon atoms, or the cycloalkyl group having 3 to 30 carbon atoms are unsubstituted or substituted with a substituent selected from the group consisting of a hydroxyl group, a halogen atom, -Q, -CH=CH 2 and -CH=CH-L 1 The group consisting of: -CH in a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 3 to 30 carbon atoms 2 - unsubstituted or substituted by -O-, carbonyl or -NL 4 - replace; or L 2 With L 3 bonded to each other to form a heterocyclic group having 1 to 10 carbon atoms, wherein the hydrogen atoms in the heterocyclic group having 1 to 10 carbon atoms are unsubstituted or replaced by L 1 , -OH, or -Q; Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, a heteroaromatic group having 5 to 10 carbon atoms, a halogen atom, -L 1 , -OH, -OL 1 , -NO 2 , -CH=CH 2 or -CH=CH-L 1 substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L 1 , -OH, -OL 1 , -NO 2 , -CH=CH 2 or -CH=CH-L 1 substituted heteroaromatic group having 5 to 10 carbon atoms; M represents potassium or sodium.

6. The method for manufacturing a color filter according to claim 1, It is characterized in that Based on 100 parts by weight of the alkali-soluble resin (C), The pigment (A-1) is 1 to 300 parts by weight; and Based on the total weight of the solid content of the photosensitive colored resin composition being 100% by weight, The pigment (A-1) is 0.5 to 50 wt %.

7. The method for manufacturing a color filter according to claim 5, It is characterized in that Based on 100 parts by weight of the alkali-soluble resin (C), The dye (B) is 1 to 90 parts by weight, The dye (B-1) is 1 to 90 parts by weight; and Based on the total weight of the solid content of the photosensitive colored resin composition being 100% by weight, The dye (B) is 0.1 wt% to 20 wt%, The dye (B-1) is present in an amount of 0.1 to 20% by weight.

8. The method for manufacturing a color filter according to claim 1, It is characterized in that Based on 100 parts by weight of the alkali-soluble resin (C), The pigment (A) is 1 to 300 parts by weight, The photopolymerizable compound (D) is 30 parts by weight to 450 parts by weight, The photoinitiator (E) is 2 to 20 parts by weight, The solvent (F) is 500 to 5000 parts by weight; and Based on the total weight of the solid content of the photosensitive colored resin composition being 100% by weight, The pigment (A) is 0.5 to 50% by weight, The alkali-soluble resin (C) is 5 to 75 wt %, The photopolymerizable compound (D) is 10 wt % to 60 wt %, The photoinitiator (E) is present in an amount of 1 wt % to 10 wt %.

9. A color filter manufactured by the color filter manufacturing method according to any one of claims 1 to 8.

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

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