TWI835669B - Manufacturing method of color filter, color filter, and liquid crystal display device - Google Patents

Abstract

The present application provides a manufacturing method of a color filter, including: coating a photosensitive colored resin composition on a substrate to obtain a coating film; exposing the coating film with ultraviolet rays through a photomask; developing the exposed coating film with a developer to obtain a pattern; and performing a post-baking treatment on the pattern at a temperature range of 200°C to 250°C for 1 minute to 15 minutes. The photosensitive colored resin composition includes a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), wherein the colorant (A) includes a first colorant (A-1), and the first colorant (A-1) is a compound represented by formula (1).

Description

Manufacturing method of color filter, color filter, and liquid crystal display device

The present invention relates to a manufacturing method of a color filter, a color filter, and a liquid crystal display device, and in particular, to a manufacturing method of a color filter, a color filter, and a liquid crystal display device.

Color display devices using color filters include (i) color liquid crystal display devices, which include: a backlight as a light source, a liquid crystal as an optical shutter, and a color adjustment function (color conversion function, color separation function, and color correction function, etc.); and (ii) a color organic electroluminescence (EL) display device including: a synthetic white organic electroluminescence (EL) light source and a color adjustment function (color conversion function, color separation function, color correction function, etc.). Color filters can also be used in image sensors (Image Sensors) such as Complementary Metal-Oxide-Semiconductor (CMOS) and Charge-Coupled Device (CCD).

Currently, known methods for manufacturing color filters include electro-deposition, printing, and photolithography. The electrocoat coating method is to form a transparent electrode with a prescribed pattern in advance; by applying voltage, a resin containing pigment dissolved or dispersed in a solvent is ionized to form a pattern. The printing method is printing methods such as offset printing using ink containing thermosetting resin or ultraviolet curing resin. The photolithography process uses a photosensitive colored resin composition in which colorants such as pigments or dyes are dispersed or dissolved in a photoresist material. In recent years, photolithography has become the mainstream color filter manufacturing method.

When forming a color filter using a photolithography process, for example, after forming a coating film of a negative photosensitive colored resin composition on a substrate, the coating film is exposed to ultraviolet rays through a mask 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).

However, although various manufacturing methods of color filters have been developed, the colored layer (pattern) in the color filter formed of the photosensitive colored resin composition has the disadvantage of poor post-baking residual film rate, and requires a relatively high A large amount of photosensitive colored resin compositions are used to produce the colored layer (pattern), which cannot achieve the effect of saving resources and being environmentally friendly.

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

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 an urgent problem that those skilled in the field currently want to solve.

The present invention provides a color filter manufacturing method, a color filter, and a liquid crystal display device. The colored layer (pattern) in the color filter produced by the color filter manufacturing method has good aftereffects. Baked film residue rate.

The invention provides a method for manufacturing a color filter, which includes: coating a photosensitive colored resin composition on a substrate to obtain a coating film; exposing the coating film to ultraviolet light through a photomask; and using a developer to The exposed coating film is developed to obtain a pattern; and the pattern is post-baked at a temperature range of 200°C to 250°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), wherein the pigment (A) includes the pigment (A) -1), and the pigment (A-1) is a compound represented by formula (1).

Formula (1) In Formula (1), A represents a p-valent organic group, in which the carbon atom directly bonded to N in the organic group does not have a π bond, and the organic group represents at least one end that is directly bonded to N. An aliphatic hydrocarbon group of a saturated aliphatic hydrocarbon group, 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- represents a q-valent heteropoly acid anion; R ¹ , R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group, where R ^2. At least one of R ³ , R ⁴ , and R ⁵ is a substituted or unsubstituted alkyl group, R ² and R ³ can be bonded to each other to form a ring structure, and R ⁴ and R ⁵ can be bonded to each other to form a ring structure. Ring structure, multiple R ¹ , R ² , R ³ , R ⁴ , and R ⁵ may each be the same or different; R ⁶ and R ⁷ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted A substituted alkoxy group, a halogen atom, or a cyano group; Ar represents a substituted or unsubstituted divalent aromatic group, and each of the plurality of Ar can be the same or different; p and q represent an integer of 2 or more; r and s represents an integer above 1; v represents 0 or 1. When v represents 0, there is no bond; t and u each independently represent an integer above 0 and below 4; t+v and u+v are above 0 and An integer below 4.

In one embodiment of the present invention, the above-mentioned R ² , R ³ , R ⁴ , and R ⁵ each independently represent a substituted or unsubstituted alkyl group.

In one embodiment of the present invention, in the above-mentioned B ^q- , the heterogeneous polyacid anion contains at least one of molybdenum (Mo) and tungsten (W).

In an embodiment of the present invention, the above-mentioned post-bake processing time is 3 minutes to 10 minutes.

In one embodiment of the present invention, the above-mentioned photosensitive colored resin composition further includes a dye (B), and the dye (B) includes a dye (B-1), wherein the dye (B-1) is of the formula ( 2) The compound shown, Formula (2) In Formula (2), R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ each independently represent 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 instead An aromatic hydrocarbon group with a carbon number of 6 to 10; 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 can each be the same or different; X represents a halogen atom; n represents 0 or 1; L ¹ represents the carbon number is an alkyl group with 1 to 10 carbon atoms or an alkyl group with a carbon number of 1 to 10 substituted by a halogen atom, in which the alkyl group with a carbon number of 1 to 10 or an alkyl group with a carbon number of 1 to 10 substituted with a halogen atom is -CH ₂ -Unsubstituted or substituted by -O-, carbonyl or -NL ⁴ -; L ⁴ represents an alkyl group with 1 to 10 carbon atoms or an alkyl group with 1 to 10 carbon atoms substituted by a halogen atom; L ² and L ³ each independently represent a linear alkyl group with 1 to 10 carbon atoms, a branched alkyl group with 3 to 10 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, or -Q; where, the number of carbon atoms The hydrogen atoms in the linear alkyl group with 1 to 10 carbon atoms, the branched chain alkyl group with 3 to 10 carbon atoms, or the cycloalkyl group with 3 to 30 carbon atoms are unsubstituted or substituted by a substituent. Selected from the group consisting of hydroxyl group, halogen atom, -Q, -CH=CH ₂ and -CH=CH-L ¹ ; linear alkyl group with 1 to 10 carbon atoms, branched chain with 3 to 10 carbon atoms -CH ₂ - in an alkyl group or a cycloalkyl group with 3 to 30 carbon atoms is unsubstituted or substituted with -O-, carbonyl group or -NL ⁴ -; or L ² and L ³ are bonded to each other to form a carbon number of 1 ~10 heterocyclic group, in which the hydrogen atom in the heterocyclic group with 1 to 10 carbon atoms is unsubstituted or substituted by L ¹ , -OH, or -Q; Q represents an aromatic hydrocarbon group with 6 to 10 carbon atoms , a heteroaryl group with a carbon number of 5 to 10, with a carbon number of 6 substituted by a halogen atom, -L ¹ , -OH, -OL ¹ , -NO ₂ , -CH=CH ₂ or -CH=CH-L ¹ ~10 aromatic hydrocarbon groups, or heteroaromatics with 5 to 10 carbon atoms substituted by halogen atoms, -L ¹ , -OH, -OL ¹ , -NO ₂ , -CH=CH ₂ or -CH=CH-L ¹ base; M represents potassium or sodium.

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

In one embodiment of the present invention, the alkali-soluble resin (C) is 100 parts by weight, 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.

In one embodiment of the present invention, based on 100 parts by weight of alkali-soluble resin (C), 100 parts by weight of alkali-soluble resin (C), 1 to 300 parts by weight of pigment (A), the photopolymerizable compound ( D) is 30 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 photosensitive colored resin composition The total solid content is 100% by weight, the pigment (A) is 0.5% to 50% by weight, the alkali-soluble resin (C) is 5% to 75% by weight, and the photopolymerizable compound (D) is 10% by weight. % to 60% by weight, and the photoinitiator (E) is 1% to 10% by weight.

The present invention also provides a color filter, which is made by the above-mentioned color filter manufacturing method.

The present invention also provides a liquid crystal display device, including the above-mentioned color filter.

Based on the above, the present invention provides a method for manufacturing a color filter by limiting the pigment (A) in the photosensitive colored resin composition to a pigment (A-1) represented by the formula (1). compound, and under the condition that the temperature of the post-baking process is 200℃~250℃, and the time of the post-baking process is limited to 1 minute~15 minutes, the colored layer (pattern) in the color filter can have good The post-baking residual film rate allows the coloring layer (pattern) to be produced with a relatively small amount of photosensitive coloring resin composition, thus achieving the effect of saving resources and being environmentally friendly.

In order to make the above-mentioned features and advantages of the present invention more obvious and understandable, embodiments are given below and described in detail as follows.

＜ Color filter and manufacturing method thereof ＞

This embodiment provides a color filter, which is made by the following color filter manufacturing method.

The method for manufacturing a color filter of this embodiment is to limit the pigment (A) in the photosensitive colored resin composition to include a compound represented by the formula (1) as the pigment (A-1), and in Under the condition that the temperature of the post-baking process is 200℃~250℃, the time of the post-baking process is limited to 1 minute to 15 minutes, so that the colored layer (pattern) in the color filter can have a good post-baked residual film The efficiency is high, so that a relatively small amount of photosensitive colored resin composition can be used to produce a colored layer (pattern), thereby achieving the effect of saving resources and being environmentally friendly.

The steps (i) to (iv) based on the photolithography process in the manufacturing method of the color filter will be described in detail below: Step (i) Coating the photosensitive colored resin composition on the substrate to obtain the coating film; Step (ii) Expose the coating film with ultraviolet light through a photomask; Step (iii) Develop the exposed coating film with a developer to obtain a pattern; and Step (iv) At 200°C~ The pattern is post-baked at a temperature of 250°C for 1 to 15 minutes to obtain the colored layer of the color filter. Step ( i )

Step (i) is to apply the photosensitive colored resin composition on the substrate to obtain a coating film.

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

The substrate in step (i) is not particularly limited, and examples thereof include transparent substrates. Specific examples of the transparent substrate include glass substrates with high transmittance for visible light, such as soda-lime glass, low-alkali borosilicate glass, and alkali-free aluminoborosilicate glass; as well as polycarbonate, polymethyl methacrylate, and polyparaphenylene. Plastic substrates such as ethylene glycol diformate and polyethylene naphthalate.

In addition, the above-mentioned substrate can be subjected to appropriate pre-processing according to requirements. Examples of pretreatment include chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum evaporation, or combinations thereof.

In addition, in order to drive the liquid crystal to emit light after panelization, 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 forming a black matrix in advance. Examples of the black matrix include, but are not limited to, multilayer films of chromium or chromium/chromium oxide, inorganic films such as titanium nitride, or resin films in which light-shielding agents are dispersed.

The coating method in step (i) is not particularly limited. Examples include coating the photosensitive colored resin composition on the substrate through coating methods such as spray coating, spin coating, slit coating, roller coating, or combinations thereof. to obtain a coating.

In addition, after the photosensitive colored resin composition is coated on the substrate, it can be dried under reduced pressure or pre-baked as necessary to volatilize the solvent.

Among them, the conditions for vacuum drying and pre-baking are not particularly limited and can be adjusted according to the types and mixing ratios of each component. Generally speaking, vacuum drying is performed at a pressure of 0 to 200mmHg for 1 second to 60 seconds, while pre-baking is performed at a temperature of 70 to 110°C for 1 minute to 15 minutes. Step ( ii )

Step (ii) is to expose the coating film to 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 an (ultra) high-pressure mercury lamp or a metal halide lamp. The exposure amount of ultraviolet rays is not particularly limited, but is preferably 1 to 1000 mJ/cm ² . Step ( iii )

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

The developer used in the development process is not particularly limited, and an alkaline developer can be used. The alkaline developer is not particularly limited, and examples thereof include aqueous solutions such as sodium carbonate and sodium hydroxide. Organic bases such as dimethylbenzylamine and triethanolamine may also be used. In addition, defoaming agents, surfactants, or combinations thereof may be added to the developer.

The method of development treatment is not particularly limited, and examples thereof include spray development, spray development, dip development, puddle development, and other methods to dissolve and remove the unexposed portion of the coating film. Step ( iv )

Step (iv) is to post-bake the pattern in a temperature range of 200°C to 250°C for 1 to 15 minutes to obtain a colored layer (color filter). It is worth noting that when the post-baking temperature is less than 1 minute or more than 15 minutes, the post-baking residual film rate of the pattern produced by the photosensitive colored resin composition is not good.

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

In addition, the heating device for the post-baking treatment is not particularly limited, and examples thereof include heating devices such as a hot plate and an oven.

On the other hand, the above steps (i) ~ (iv) do not necessarily need to be performed continuously, and other steps can be inserted into each step as required. For example, after step (i), water-soluble resin or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is coated on the coating film and dried to increase ultraviolet exposure sensitivity, thereby forming an oxygen barrier. After the poly film is obtained, proceed to step (ii). In addition, after step (iii), the pattern can be further exposed to ultraviolet light to promote the photo-crosslinking reaction before step (iv) is performed.

The color filter produced by the color filter manufacturing method of this embodiment can be applied to, but is not limited to, liquid crystal display devices. ＜ Liquid crystal display device and manufacturing method thereof ＞

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

When used in a liquid crystal display device, a cover film, columnar spacers, a transparent conductive film, a liquid crystal alignment film, or a combination thereof can be formed on the color filter as needed.

Specifically, the liquid crystal display element of this embodiment can be manufactured as follows.

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 substrates. Then, alignment films are further respectively provided on one or two of the substrates. Next, liquid crystal is injected between the two substrates.

There are no special restrictions on the liquid crystal display device. For example, it can be applied to twisted nematic (TN) type, super twisted nematic (Super Twisted Nematic, STN) type, in-plane switching (In Plane Switching, IPS) panel, vertical alignment Liquid crystal display modes that use color filters for coloring, such as Vertical Alignment (VA) panels and optically compensated birefringence mode (OCB) panels. ＜ Photosensitive colored resin composition ＞

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 pigment (A-1). In addition, if necessary, the photosensitive colored resin composition of this embodiment may selectively include dye (B), additive (G), or a combination thereof. Each component of the photosensitive colored resin composition used in this embodiment will be described in detail below:

In the following, (meth)acrylic acid represents acrylic acid and/or methacrylic acid, and (meth)acrylate represents acrylate and/or methacrylate; similarly, (meth)acrylyl group represents Acrylyl group and/or methacrylamide group; (meth)acrylamide represents acrylamide and/or methacrylamide. Pigments ( A )

Pigment (A) may include pigment (A-1). In addition, the pigment (A) may include other pigments (A-2) in addition to the pigment (A-1). Pigments ( A-1 )

Pigment (A-1) is a compound represented by formula (1). Formula (1) In Formula (1), A represents a p-valent organic group, in which the carbon atom directly bonded to N in the organic group does not have a π bond, and the organic group represents at least one end that is directly bonded to N. An aliphatic hydrocarbon group of a saturated aliphatic hydrocarbon group, 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- represents a q-valent heteropoly acid anion (heteropoly acid); R ¹ , R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group, where R ² , R ³ , R ⁴ , and at least one of R ⁵ is a substituted or unsubstituted alkyl group, R ² and R ³ can be bonded to each other to form a ring structure, and R ⁴ and R ⁵ can be bonded to each other to form a ring. structure, multiple R ¹ , R ² , R ³ , R ⁴ , and R ⁵ may each be the same or different; R ⁶ and R ⁷ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted Substituted alkoxy group, halogen atom, or cyano group; Ar represents a substituted or unsubstituted divalent aromatic group, and multiple Ar can each be the same or different; p and q represent an integer of 2 or more; r and s represents an integer above 1; v represents 0 or 1. When v represents 0, there is no bond; t and u each independently represent an integer above 0 and below 4; t+v and u+v are above 0 and 4 The following integers.

The p-valent organic group represented by A in formula (1) has no π bond with the carbon atom directly bonded to the nitrogen atom (N), and the organic group represents at least saturated at the end directly bonded to N. An aliphatic hydrocarbon group of an aliphatic hydrocarbon group, or an aromatic group having said aliphatic hydrocarbon group, wherein the carbon chain of the aliphatic hydrocarbon group may contain oxygen atoms (O), sulfur atoms (S), nitrogen atoms (N), aromatic groups The carbon chain of 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 hue or transmittance of the cationic color-developing part are not affected by the bonding group A or other color-developing parts, and can be maintained Same color as the monomer.

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

In A of the formula (1), examples of the aromatic group having the aliphatic hydrocarbon group include monocyclic or polycyclic aromatic groups having at least one aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the terminal directly bonded to N. , which may have substituents, or may be a heterocyclic ring containing O, S, and N.

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

In A in formula (1), from the viewpoint of the rigidity of the skeleton, the cyclic aliphatic hydrocarbon group of A is preferably a bridged alicyclic hydrocarbon group. A bridged alicyclic hydrocarbon group refers to a polycyclic aliphatic hydrocarbon group having a cross-linked structure in an aliphatic ring and a polycyclic structure. Examples of bridged alicyclic hydrocarbon groups include: norbornane, bicyclo[2.2.2]octane, adamantane, etc. The bridged alicyclic hydrocarbon group is preferably norbornane. Examples of the aromatic group include a group containing a benzene ring and a naphthalene ring, and a group containing a benzene ring is preferred. For example, when A is a divalent organic group, examples include a linear, branched, or cyclic alkylene group having a carbon number of 1 to 20, or a xylylene group having a carbon number of 1 to The alkylene group of 20 is substituted by 2 aromatic groups, etc.

In A in the formula (1), the valence p is the number of chromogenic cationic sites constituting the cation, and p represents an integer of 2 or more. In this lake pigment, from the viewpoint of heat resistance, the valence p of the cation is preferably 2 or more, more preferably 3 or more. The upper limit of p is not particularly limited. From the viewpoint of ease of production, p is preferably 4 or less, more preferably 3 or less.

R ¹ , R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, wherein at least one of R ² , R ³ , R ⁴ , and R ⁵ is a substituted or unsubstituted alkyl group. Moreover, it is preferable that R ² , R ³ , R ⁴ and R ⁵ each independently represent a substituted or unsubstituted alkyl group. When R ² , R ³ , R ⁴ , and R ⁵ each independently represent a substituted or unsubstituted alkyl group, the pattern produced by the photosensitive colored resin composition has a better post-baking residual film rate.

The alkyl group in R ¹ , R ² , R ³ , R ⁴ , and R ⁵ is not particularly limited. Examples include linear or branched alkyl groups with a carbon number of 1 to 20. Preferably, the alkyl group has a carbon number of 1. A straight-chain or branched alkyl group with a carbon number of ~8, more preferably a straight-chain or branched alkyl group with a carbon number of 1-5, particularly preferably an ethyl group or a methyl group. The substituent that the alkyl group may have is not particularly limited, and examples thereof include a halogen atom, a hydroxyl group, an alkoxy group, and the like.

From the viewpoint of chemical stability, it is preferred that R ¹ , R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or R ² and R ³ each other. The bonds form a ring structure, and R ⁴ and R ⁵ bond to each other to form a ring structure, wherein the ring structure may include a pyrrolidine ring, a piperidine ring, or a morpholine ring.

R ¹ , R ² , R ³ , R ⁴ , and R ⁵ can each independently form the above structure. That is to say, multiple R ¹ , R ² , R ³ , R ⁴ , and R ⁵ can each be the same or different. .

R ⁶ and R ⁷ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a halogen atom, or a cyano group. The substituted or unsubstituted alkyl group in R ⁶ and R ⁷ is not particularly limited. It is preferably a linear or branched alkyl group with a carbon number of 1 to 8, and more preferably a linear or branched alkyl group with a carbon number of 1 to 4. alkyl. Examples of alkyl groups with 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl. These groups can be linear or branched. The substituent that the alkyl group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, or a combination thereof.

In addition, the substituted or unsubstituted alkoxy group in R ⁶ and R ⁷ is not particularly limited, but is preferably a linear or branched alkoxy group with a carbon number of 1 to 8, and more preferably a carbon number of 1~4 alkoxy groups. Examples of alkoxy groups having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy, and these groups may be linear or branched. The substituent that the alkoxy group may have is not particularly limited, and examples thereof include an aryl group, a halogen atom, a hydroxyl group, an alkoxy group, and the like.

Examples of the halogen atom of R ⁶ and R ⁷ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a combination thereof.

The substitution numbers of R ⁶ and R ⁷ , that is, t and u each independently represent an integer from 0 to 4, preferably from 0 to 2, more preferably from 0 to 1. t+v and u+v are integers from 0 to 4. When t and u are two or more, each of the plurality of t and u may be the same or different.

In addition, when v represents 0, there is no bonding, and the compound represented by formula (1) has a triarylmethane skeleton. Among them, R ⁶ and R ⁷ can be substituted at any position of the triarylmethane skeleton or the aromatic ring having a resonance structure within the skeleton. Among them, the preferred ones are represented by -NR ² R ³ or -NR ⁴ R ⁵ The substituted position of the amine group is based on the meta position.

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

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

Multiple R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ and Ar may be the same or different in one molecule. Through the combination of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ and Ar, the required color can be adjusted.

In the compound represented by formula (1), from the viewpoint of high brightness and excellent heat resistance, B ^q- represents a q-valent heterogeneous multiple acid anion. The heterogeneous multiple acid anions can be expressed as (Y ₁ M _{e Of} ) ^q- . In the above ionic formula, M represents a polyatom, Y represents a heteroatom, e represents the composition ratio of polyatoms, 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 hetero atom Y include silicon (Si), phosphorus (P), arsenic (As), sulfur (S), iron (Fe), cobalt (Co), and the like.

Among them, in B ^q- , the heterogeneous multiple acid anion preferably contains at least one of molybdenum (Mo) and tungsten (W), and more preferably, the heterogeneous multiple acid anion contains at least q valence of tungsten.

r in formula (1) represents the number of cations, and s represents the number of anions. r and s represent integers above 1. When r represents 2 or more, a plurality of cations in the formula (1) can be used alone or in combination. In addition, when s is 2 or more, a plurality of anions in the formula (1) can be used alone or in combination.

v in Formula (1) represents an integer of 0 or 1. When v represents 0, there is no bonding, and the main structure of formula (1) is a triarylmethane skeleton. When v represents 1, the main structure of formula (1) is the xanthene skeleton. Each of the multiple v's can be the same or different. Among the compounds represented by formula (1), it is preferable that they contain a triarylmethane skeleton.

In addition, the compound represented by formula (1) can be prepared by referring to the specification of International Publication No. 2012/144520, for example.

The above-mentioned pigments (A-1) can be used alone or in combination.

Specific examples of the compound represented by formula (1) may include at least one of compound (1-1) to compound (1-20). Compounds (1-1) to (1-20) each contain one cation and one heterogeneous multiple acid anion.

Preferable examples of the compound represented by formula (1) include compound (1-1) to compound (1-4), compound (1-6) to compound (1-7), compound (1-10) to compound ( At least one of the compounds represented by compound (1-11), compound (1-14), and compound (1-17).

Compound (1-1) Compound (1-2) Compounds (1-3) Compounds (1-4) Compounds (1-5) Compounds (1-6) Compounds (1-7) Compounds (1-8) Compounds (1-9) Compounds (1-10) Compounds (1-11) Compounds (1-12) Compounds (1-13) Compounds (1-14) Compounds (1-15) Compounds (1-16) Compounds (1-17) Compounds (1-18) Compounds (1-19) Compounds (1-20)

When the photosensitive colored resin composition does not contain the pigment (A-1), the post-baking residual film rate of the pattern produced by the photosensitive colored resin composition is unsatisfactory.

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

In this embodiment, based on the total weight of the solid content of the photosensitive colored resin composition being 100% by weight, the pigment (A-1) can be 0.5% to 50% by weight, preferably 1% to 45% by weight. , more preferably 5% to 40% by weight. Other pigments ( A-2 )

In this embodiment, the pigment (A) may further include other pigments (A-2). Other pigments (A-2) may be inorganic pigments, organic pigments, or combinations thereof.

Inorganic pigments can be metal compounds such as metal oxides and metal complex salts. Among them, inorganic pigments include iron (Fe), cobalt (Co), aluminum (Al), cadmium (Cd), lead (Pb), copper (Cu), titanium (Ti), magnesium (Mg), and chromium (Cr). , zinc (Zn), antimony (Sb) and other metal oxides, complex oxides of the aforementioned metals, metal salts, or combinations thereof.

Specific examples of organic pigments include C.I. 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; C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43 , 46, 49, 51, 61, 63, 64, 71, 73; C.I. 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: l, 48: 2, 48: 3, 48: 4, 49: l, 49: 2. 50:1, 52:l, 53:l, 57, 57:l, 57:2, 58:2, 58:4, 60:l, 63:l, 63:2, 64:l, 81: l, 83, 88, 90: l, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 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, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; C.I. Pigment Violet l, 14, 19, 23, 29, 32, 33, 36, 37, 38, 39, 40, 50; C.I. Pigment Blue l, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 21, 22, 60, 61, 64, 66; C.I. Pigment Green 7, 36, 37 , 42, 58; C.I. Pigment Brown 23, 25, 28; C.I. Pigment Black 1, 7; or combinations thereof.

The above-mentioned other pigments (A-2) can be used individually or in mixture of multiple types.

The other pigment (A-2) is preferably C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, or a combination thereof.

The average particle diameter of other pigments (A-2) may be 10 nm to 200 nm, preferably 20 nm to 150 nm, more preferably 30 nm to 130 nm.

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

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

In this embodiment, based on the total weight of the solid content of the photosensitive colored resin composition being 100% by weight, the pigment (A) can be 0.5% to 50% by weight, preferably 1% to 45% by weight. More preferably, it is 5% by weight to 40% by weight.

In the photosensitive coloring resin composition of this embodiment, the pigment (A) is preferably used by being dispersed in a solvent by means of a dispersant. In this embodiment, the dispersant can be appropriately selected from known dispersants. The dispersant can include cationic surfactants, anionic surfactants, non-ionic 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 viewpoint of being able to disperse uniformly and finely, the surfactant is preferably a polymer dispersant.

Polymer dispersants include (co)polymers of unsaturated carboxylic acid esters such as polyacrylate; (partial) amine salts, (partial) ammonium salts or (co)polymers of unsaturated carboxylic acid esters such as polyacrylic acid. Parts) alkylamine salts; (co)polymers of hydroxyl-containing unsaturated carboxylic acid esters such as hydroxyl-containing polyacrylates or modified products of the above compounds; polyurethanes; unsaturated polyamides; Polysiloxanes; long-chain polyaminoamide phosphates; polyethyleneimine derivatives (carboxylamines obtained by the reaction of poly(lower alkyleneimine) and polyesters containing free carboxyl groups) amine or its base); polyallylamine derivatives (polyallylamine and 3 types of co-condensate (polyesteramide) selected from polyester, polyamide or ester and amide containing free carboxyl groups A reaction product obtained by reacting one or more compounds among the compounds), or a combination thereof.

From the viewpoint that the pigment (A) can be preferably dispersed and the dispersion stability is good, the polymer dispersant is preferably a polymer dispersant containing nitrogen atoms in the main chain or side chain and having an amine valence.

Specific examples of polymer dispersants containing nitrogen atoms in the main chain or side chain are as follows.

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 of the above are Bi (manufactured by BYK-Chemie), etc.

Examples of commercially available polyurethanes include Disperbyk 161 (manufactured by BYK-Chemie) and the like.

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

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

Commercially available products of polyethyleneimine derivatives include Solsperse 33500 (manufactured by Lubrizol Corporation of Japan) and the like.

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, Dysperbyk 2050 ( The above are all manufactured by BYK-Chemie); EFKA4046, EFKA 4047 (the above are all manufactured by EFKA Chemicals Co.); Solsperse 12000, Solsperse 13250, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 24000SC, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 33500, Solsperse 35200, Solsperse 37500 (the above are all manufactured by Lubrizol Corporation of Japan) ); Ajisper PB711, Ajisper 823, Ajisper 880 ( The above are all manufactured by Ajinomoto Fine-Techno Co., Ltd.), etc.

The amount of dispersant used is not particularly limited and can be adjusted appropriately according to needs. Dye ( B )

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

The dye (B-1) is a compound represented by formula (2). Formula (2) In Formula (2), R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ each independently represent 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 instead An aromatic hydrocarbon group with a carbon number of 6 to 10; 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 can each be the same or different; X represents a halogen atom; n represents 0 or 1; L ¹ represents the carbon number is an alkyl group with 1 to 10 carbon atoms or an alkyl group with a carbon number of 1 to 10 substituted by a halogen atom, in which the alkyl group with a carbon number of 1 to 10 or an alkyl group with a carbon number of 1 to 10 substituted with a halogen atom is -CH ₂ -Unsubstituted or substituted by -O-, carbonyl or -NL ⁴ -; L ⁴ represents an alkyl group with 1 to 10 carbon atoms or an alkyl group with 1 to 10 carbon atoms substituted by a halogen atom; L ² and L ³ each independently represent a linear alkyl group with 1 to 10 carbon atoms, a branched alkyl group with 3 to 10 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, or -Q; where, the number of carbon atoms The hydrogen atoms in the linear alkyl group with 1 to 10 carbon atoms, the branched chain alkyl group with 3 to 10 carbon atoms, or the cycloalkyl group with 3 to 30 carbon atoms are unsubstituted or substituted by a substituent. Selected from the group consisting of hydroxyl, halogen atom, -Q, -CH=CH ₂ and -CH=CH-L ¹ ; linear alkyl group with 1 to 10 carbon atoms, branched chain with 3 to 10 carbon atoms -CH ₂ - in an alkyl group or a cycloalkyl group with 3 to 30 carbon atoms is unsubstituted or substituted with -O-, carbonyl group or -NL ⁴ -; or L ² and L ³ are bonded to each other to form a carbon number of 1 ~10 heterocyclic groups, in which the hydrogen atoms in the heterocyclic groups with 1 to 10 carbon atoms are unsubstituted or substituted by L ¹ , -OH, or -Q; Q represents an aromatic hydrocarbon group with 6 to 10 carbon atoms , a heteroaromatic group with a carbon number of 5 to 10, with a carbon number of 6 substituted by a halogen atom, -L ¹ , -OH, -OL ¹ , -NO ₂ , -CH=CH ₂ or -CH=CH-L ¹ ~10 aromatic hydrocarbon groups, or heteroaromatics with 5 to 10 carbon atoms substituted by halogen atoms, -L ¹ , -OH, -OL ¹ , -NO ₂ , -CH=CH ₂ or -CH=CH-L ¹ base; M represents potassium or sodium.

In formula (2), L ¹ preferably includes but is not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclo Pentyl, 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.

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

In formula (2), -SO ₃ L ¹ preferably includes but is not limited to methanesulfonyl, ethanesulfonyl, hexanesulfonyl, or decylsulfonyl. (decanesulfonyl).

In formula (2), -COOL ¹ includes but is not limited to methyloxycarbonyl, ethyloxycarbonyl, 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, hexyloxy propoxycarbonyl, 2-ethylhexyloxypropoxycarbonyl, or methoxyhexyloxycarbonyl.

In formula (2), -SO ₂ NHL ² preferably includes but is not limited to sulfamoyl, methylsulfamoyl, ethylsulfamoyl, propylsulfamoyl, and isopropyl Aminesulfonyl, butylaminesulfonyl, isobutylaminesulfonyl, amylaminesulfonyl, isopentylaminesulfonyl, neopentylaminesulfonyl, cyclopentylaminesulfonyl , hexylamine sulfonyl, cyclohexylamine sulfonyl, heptylamine sulfonyl, cycloheptylamine sulfonyl, octylamine sulfonyl, cyclooctylamine sulfonyl, 2-ethylhexylamine Sulfonyl, nonylaminesulfonyl, decylaminesulfonyl, tricyclic [5.3.0.0 ^3,10 ] decylaminesulfonyl, methoxypropylaminesulfonyl, hexyloxypropyl Aminesulfonyl, 2-ethylhexyloxypropylaminesulfonyl, methoxyhexylaminesulfonyl, epoxypropylaminesulfonyl, 1,5-dimethylhexylaminesulfonyl , propoxypropylaminesulfonyl, isopropoxypropylaminesulfonyl, 3-phenyl-1-methylpropylaminesulfonyl,, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , (R ^a represents an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, an alkyl group with 1 to 3 carbon atoms substituted by a halogen atom, or an alkyl group with 1 to 3 carbon atoms substituted with a halogen atom. 3 alkoxy group), , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , (R ^b represents an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, an alkyl group with 1 to 3 carbon atoms substituted by a halogen atom, or an alkyl group with 1 to 3 carbon atoms substituted with a halogen atom. 3 alkoxy group), , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,or .

Dyes (B-1) include but are not limited to compounds represented by formula (2-1), compounds represented by formula (2-2), compounds represented by formula (2-3), compounds represented by formula (2-4) compounds shown, or combinations thereof.

Formula (2-1) In Formula (2-1), R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom, -L ¹ , an aromatic hydrocarbon group with 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 substituted aromatic hydrocarbon group with 6 to 10 carbon atoms; R ¹⁷ represents a hydrogen atom, -SO ₃ ^- , -SO ₃ H, -SO ₂ NHL ² or -SO ₂ NL ² L ³ ; R ¹⁸ represents -SO ₃ ^- , -SO ₃ H, -SO ₂ NHL ² or -SO ₂ NL ² L ³ ; X represents a halogen atom; n represents 0 or 1.

Formula (2-2) In Formula (2-2), R ¹⁹ , R ²⁰ , R ²¹ , and R ²² each independently represent a hydrogen atom, -L ⁵ , an aromatic hydrocarbon group with 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 Number of substituted carbons is an aromatic hydrocarbon group of 6 to 10; R ²³ represents -SO ₃ ^- , -SO ₃ Na, -COOH, -COOL ⁵ , -SO ₃ H, or -SO ₂ NHL ⁷ ; u ¹ represents an integer from 0 to 5, when When u ¹ represents 2 to 5, multiple u ¹ can each be the same or different; X represents a halogen atom; n represents 0 or 1; L ⁵ represents an alkyl group with a carbon number of 1 to 10, or a halogen atom or - OL ⁶ substitutes an alkyl group with 1 to 10 carbon atoms; L ⁶ represents an alkyl group with 1 to 10 carbon atoms; and L ⁷ represents a hydrogen atom, -L ⁵ , -COOL ⁵ , and an aromatic group with 6 to 10 carbon atoms. Hydrocarbon group, or aromatic hydrocarbon group with 6 to 10 carbon atoms substituted by -L ⁵ or -OL ⁵ .

Formula (2-3) In Formula (2-3), R ²⁴ and R ²⁵ each independently represent a phenyl group, or a halogen atom, -L ⁵ , -OL ⁵ , -COOL ⁵ , -SO ₃ L ⁵ , or - SO ₂ NHL ⁷ substituted phenyl group; R ²⁶ represents -SO ₃ ^- or -SO ₂ NHL ⁷ ; R ²⁷ represents a hydrogen atom, -SO ₃ ^- or -SO ₂ NHL ⁷ ; X represents a halogen atom; n represents 0 Or 1; L ⁵ represents an alkyl group with 1 to 10 carbon atoms, or an alkyl group with 1 to 10 carbon atoms substituted by a halogen atom or -OL ⁶ ; L ⁶ represents an alkyl group with 1 to 10 carbon atoms; and L ⁷ represents a hydrogen atom, -L ⁵ , -COOL ⁵ , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms substituted by -L ⁵ or -OL ⁵ .

Formula (2-4) In Formula (2-4), R ²⁸ and R ²⁹ each independently represent a phenyl group, or a phenyl group substituted by a halogen atom, -L ⁵ , or -SO ₂ NHL ⁷ ; R ³⁰ represents -SO ₃ ^{- ,} or ^-SO ₂ NHL ⁷ ; an alkyl group; L ⁶ represents an alkyl group with a carbon number of 1 to 10; and L ⁷ represents a hydrogen atom, -L ⁵ , -COOL ⁵ , an aromatic hydrocarbon group with a carbon number of 6 to 10, or via -L ⁵ or -OL ^5- substituted aromatic hydrocarbon group with 6 to 10 carbon atoms.

The above dyes (B-1) can generally be used alone or in combination.

Specific compounds of dye (B-1) include, but are not limited to, compounds represented by formula (i-1) to formula (i-31), or combinations thereof.

Formula (i-1) In formula (i-1), R ^c and R ^d each independently represent a hydrogen atom, -SO ₃ ^- , -COOH, or -SO ₂ NHL ⁸ ; L ⁸ represents 2-ethylhexyl; X represents a halogen atom; n represents 0 or 1.

Formula (i-2) In formula (i-2), R ^e represents a hydrogen atom, -SO ₃ ^- , -COOH, or -SO ₂ NHL ⁸ ; L ⁸ represents 2-ethylhexyl; X represents a halogen atom; n Represents 0 or 1.

Formula (i-3) In formula (i-3), R ^e represents a hydrogen atom, -SO ₃ ^- , -COOH, or -SO ₂ NHL ⁸ ; L ⁸ represents 2-ethylhexyl; X represents a halogen atom; n Represents 0 or 1.

Formula (i-4) In formula (i-4), R ^f , R ^g and R ^h each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHL ⁸ ; L ⁸ represents 2-ethylhexyl .

Formula (i-5) In formula (i-5), R ^f , R ^g and R ^h each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHL ⁸ ; L ⁸ represents 2-ethylhexyl .

Formula (i-6) In Formula (i-6), R ⁱ , R ^j and R ^k each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHL ⁸ ; L ⁸ represents 2- Ethylhexyl.

Formula (i-7) In Formula (i-7), R ⁱ , R ^j and R ^k each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHL ⁸ ; L ⁸ represents 2- Ethylhexyl.

Formula (i-8) In formula (i-8), R ^l , R ^m and R ⁿ each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHL ⁸ ; L ⁸ represents 2-ethylhexyl .

Formula (i-9) In formula (i-9), R ^l , R ^m and R ⁿ each independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHL ⁸ ; L ⁸ represents 2-ethylhexyl .

Formula (i-10) In Formula (i-10), R ^p , R ^q and R ^r each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHL ⁸ ; L ⁸ represents 2- Ethylhexyl.

Formula (i-11) In Formula (i-11), R ^p , R ^q and R ^r each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHL ⁸ ; L ⁸ represents 2- Ethylhexyl.

Formula (i-12)

Formula (i-13)

Formula (i-14)

Formula (i-15)

Formula (i-16)

Formula (i-17)

Formula (i-18)

Formula (i-19)

Formula (i-20)

Formula (i-21)

Formula (i-22)

Formula (i-23)

Formula (i-24)

Formula (i-25)

Formula (i-26)

Formula (i-27)

Formula (i-28)

Formula (i-29)

Formula (i-30)

Formula (i-31)

The above-mentioned dyes (B-1) can be used alone or in combination.

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

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

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

In this embodiment, based on the total weight of the solid content of the photosensitive colored resin composition being 100% by weight, the dye (B-1) may be 0.1% to 20% by weight, preferably 0.5% to 18% by weight. %, more preferably 1 to 15% by weight. Other dyes ( B-2 )

The photosensitive colored resin composition may further include other dyes (B-2) in addition to the dye (B-1). Other dyes (B-2) include, but are not limited to, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, or combinations thereof.

Azo dyes include but are not limited to C.I. 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, medium red 7, medium yellow 5, medium Black 7, or its combination.

Anthraquinone dyes include, but are not limited to, C.I. Batblue 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.

Phthalocyanine dyes include but are not limited to C.I. Basic Blue 5 and the like.

Quinone imine dyes include, but are not limited to, C.I. Basic Blue 3, C.I. Basic Blue 9, or combinations thereof.

Quinoline dyes C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Disperse Yellow 64, or combinations thereof.

Nitro dyes include, but are not limited to, C.I. Acid Yellow 1, Acid Orange 3, Disperse Yellow 42, or combinations thereof.

The above-mentioned other dyes (B-2) can be used alone or in combination.

Other dyes (B-2) preferably include C.I. Acid Red 37, C.I. Acid Blue 29, or combinations thereof.

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

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

In this embodiment, based on the total weight of the solid content of the photosensitive colored resin composition being 100% by weight, the dye (B) may be 0.1% to 20% by weight, preferably 0.5% to 18% by weight. More preferably, it is 1% by weight to 15% by weight. Alkali-soluble resin ( C )

The alkali-soluble resin (C) of this embodiment may include the 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). First base soluble resin ( C-1 )

The first alkali-soluble resin (C-1) in this embodiment is composed of a carboxylic acid group-containing ethylenically unsaturated monomer (c-1-1) and other copolymerizable ethylenically unsaturated monomers (c-1 -2) Obtained from copolymerization.

Carboxylic acid group-containing ethylenically unsaturated monomers (c-1-1) can be used alone or in mixture, and carboxylic acid group-containing ethylenically unsaturated monomers include but are not limited to acrylic acid, methacrylic acid (methacrylic acid, referred to as MAA), crotonic acid, alpha-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-methacryloyloxyethyl succinate, or 2-methacryloyloxyethyl succinate unsaturated monocarboxylic acids such as monoester (abbreviated as HOMS); unsaturated dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride. ); unsaturated polycarboxylic acids (anhydrides) with more than three carboxylic acid groups. The ethylenically unsaturated monomer containing a carboxylic acid group preferably includes acrylic acid, methacrylic acid, 2-acrylyl ethoxy succinate, 2-methacryl ethoxy succinate, or a combination thereof . The carboxylic acid group-containing ethylenically unsaturated monomer is more preferably 2-acrylyl ethoxy succinate, 2-methacryl ethoxy succinate, or a combination thereof.

In this embodiment, the carboxylic acid group-containing ethylenically unsaturated monomer (c-1-1) based on the first alkali-soluble resin (C-1) and other copolymerizable ethylenically unsaturated monomers (c -1-2) is used in an amount of 100 parts by weight, and the carboxylic acid group-containing ethylenically unsaturated monomer (c-1-1) is used in an amount of 10 to 90 parts by weight, preferably 15 to 85 parts by weight, More preferably, it is 20 to 80 parts by weight.

Other copolymerizable ethylenically unsaturated monomers (c-1-2) can be used alone or in mixture, and other copolymerizable ethylenically unsaturated monomers (c-1-2) include but are not limited to styrene ( styrene (SM for short), α-methylstyrene, vinyltoluene, p-chlorostyrene, methoxystyrene and other aromatic vinyl compounds; N-phenylmaleimide (N-phenylmaleimide for short) PMI), nitrogen-o-hydroxyphenylmaleimide, nitrogen-m-hydroxyphenylmaleimide, nitrogen-p-hydroxyphenylmaleimide, nitrogen-o-methylphenyl Maleimide, nitrogen-m-methylphenylmaleimide, nitrogen-p-methylphenylmaleimide, nitrogen-o-methoxyphenylmaleimide, nitrogen - Maleimines such as m-methoxyphenylmaleimide, nitrogen-p-methoxyphenylmaleimide, nitrogen-cyclohexylmaleimide, etc.; methyl acrylate (methyl acrylate, MA for short), methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-propyl acrylate Butyl ester, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, second butyl acrylate, second butyl methacrylate, third butyl acrylate, third butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, acrylic acid 2 -Hydroxybutyl, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate , Allyl methacrylate, benzyl acrylate, benzyl methacrylate (BzMA), phenyl acrylate, phenyl methacrylate, triethylene glycol methoxy acrylate, trimethacrylate Ethylene glycol methoxyester, dodecyl methacrylate, myristyl methacrylate, cetyl methacrylate, stearyl methacrylate, eicosyl methacrylate esters, unsaturated carboxylic acid esters such as behenyl methacrylate, dicyclopentenyloxyethyl acrylate (DCPOA), etc.; acrylic acid-nitrogen, nitrogen-dimethylaminoethyl ester, Methacrylic acid - nitrogen, nitrogen - dimethylaminoethyl ester, acrylic acid - nitrogen, nitrogen - diethylaminopropyl ester, methacrylic acid - nitrogen, nitrogen - dimethylaminopropyl ester, acrylic acid nitrogen, nitrogen -Dibutylaminopropyl, nitrogen-iso-butylaminoethyl methacrylate; 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.; vinyl methyl ether, vinyl ethyl ether, allyl epoxy propyl ether, methallyl epoxy propyl ether unsaturated ethers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylene cyanide and other nitrile vinyl compounds; acrylamide, methacrylamide, α-chloroacrylamide, Unsaturated amides such as nitrogen-hydroxyethyl acrylamide and nitrogen-hydroxyethyl methacrylamide; aliphatic conjugation of 1,3-butadiene, isoprene, chlorinated butadiene, etc. Dienes; or combinations thereof.

Other copolymerizable ethylenically unsaturated monomers (c-1-2) preferably include styrene, nitrogen-phenyl maleimide, methyl acrylate, methyl methacrylate, and 2-hydroxyethyl acrylate. ester, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, dicyclopentenyloxyethyl acrylate, or combinations thereof.

In this embodiment, the carboxylic acid group-containing ethylenically unsaturated monomer (c-1-1) based on the first alkali-soluble resin (C-1) and other copolymerizable ethylenically unsaturated monomers (c -1-2) is used in an amount of 100 parts by weight, and other copolymerizable ethylenically unsaturated monomers (c-1-2) are used in an amount of 10 to 90 parts by weight, preferably 15 to 85 parts by weight, More preferably, it is 20 to 80 parts by weight.

The preparation method of the first alkali-soluble resin (C-1) is not particularly limited, and an appropriate polymerization method can be selected according to requirements. Examples of the polymerization method include solution polymerization. In addition to the required monomer, the reaction solution of the alkali-soluble resin (B) may also include a solvent, a initiator, and the like. The solvent can be used alone or in mixture, 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 methyl 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 (PGMEA), propylene glycol ethyl ether acetate, etc. (Poly)alkylene glycol monoalkyl ether acetates; other ethers such as diglyme, diglyme methyl ether, diglyme diethyl ether, tetrahydrofuran, etc.; methyl ethyl ketone, cyclohexanone, Ketones such as 2-heptanone and 3-heptanone; lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; methyl 2-hydroxy-2-methylpropionate, 2 -Hydroxy-ethyl 2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Ester (ethyl 3-ethoxypropionate, referred to as EEP), ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylacetic acid Ester, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isopentyl acetate Ester, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetic acid Other esters such as methyl ester, ethyl acetate acetate, and ethyl 2-methoxybutyrate; aromatic hydrocarbons such as toluene and xylene; nitrogen-methylpyrrolidone, nitrogen, nitrogen-dimethyl Formamide, or nitrogen, nitrogen-dimethylacetamide and other amide compounds. 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.

The initiator is generally a free radical polymerization initiator, specific examples include: 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 Azo compounds such as butyronitrile (AMBN); peroxy compounds such as dibenzoyl peroxide.

The above-mentioned first alkali-soluble resin (C-1) can be used alone or in combination of multiple types.

In addition, the polystyrene-converted number average molecular weight of the first alkali-soluble resin (C-1) measured by Gel Permeation Chromatography (GPC) is 1,000 to 35,000, preferably 3,000 to 30,000, more preferably 3,000 to 30,000. The best range is 5,000 to 25,000.

In this embodiment, the usage amount of the alkali-soluble resin (C) is 100 parts by weight, and the usage amount of the first alkali-soluble resin (C-1) is 10 to 100 parts by weight, preferably 20 to 90 parts by weight, More preferably, it is 30 to 80 parts by weight. Second alkali soluble resin ( C-2 )

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

The epoxy compound (c-2-1) having at least two epoxy groups may have a structure represented by the following formula (3-1) or the following formula (3-2). Here, the description that "the epoxy compound (c-2-1) may have a structure represented by the following formula (3-1) or the following formula (3-2)" also covers the structure represented by the following formula (3) A case where a compound having a structure represented by -1) and a compound having a structure represented by the following formula (3-2) coexist as the epoxy compound (c-2-1). Specifically, the aforementioned epoxy compound (c-2-1) having at least two epoxy groups has, for example, a structure represented by the following formula (3-1):

Formula (3-1) In Formula (3-1), R ^{1c ,} R ^{2c ,} R ^3c and R ^4c each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. As for an alkoxy group, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 6 to 12 carbon atoms, R ^{1c ,} R ^{2c ,} R ^3c and R ^4c may each be the same or different.

The epoxy compound (c-2-1) having at least two epoxy groups of the aforementioned formula (3-1) may include an epoxy compound (c-2-1) obtained by the reaction of a bisphenol fluorene compound and an epihalohydrin. Epoxy group-containing bisphenol fluorene type compound, but not limited to this.

Specific examples of the above-mentioned bisphenol-fluorene compounds include, but are not limited to: 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 4-hydroxy-3-methylphenyl)fluorene (9,9-bis(4-hydroxy-3-methylphenyl)fluorene), 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene (9,9-bis(4-hydroxy-3-methylphenyl)fluorene) 9-bis(4-hydroxy-3-chlorophenyl) fluorene), 9,9-bis(4-hydroxy-3-bromophenyl)fluorene (9,9-bis(4-hydroxy-3-bromophenyl)fluorene), 9,9-bis(4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis(4-hydroxy-3-methoxy) Phenyl)fluorene (9,9-bis (4-hydroxy-3-methoxyphenyl)fluorene), 9,9-bis (4-hydroxy-3,5-dimethylphenyl)fluorene (9,9-bis( 4-hydroxy-3,5-dimethylphenyl)fluorene), 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorene (9,9-bis(4-hydroxy-3,5-dichlorophenyl) fluorene), 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene (9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene), or combinations thereof.

The above-mentioned halogenated propylene oxide (epihalohydrin) may include, but is not limited to, 3-chloro-1,2-epoxypropane (epichlorohydrin), 3-bromo-1,2-epoxypropane (epibromohydrin), or combinations thereof.

The above-mentioned bisphenol-fluorene-type compounds containing epoxy groups obtained by the reaction of bisphenol-fluorene-type compounds and 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 S.M.S Technology Co., Ltd. Products: such as SMS-F9PhPG, SMS-F9CrG, SMS-F914PG; or combinations thereof.

Secondly, the epoxy compound (c-2-1) with at least two epoxy groups may also have a structure represented by the following formula (3-2):

Formula (3-2) In Formula (3-2), R ^5c to R ^18c each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, or an aromatic group with 6 to 15 carbon atoms. R ^5c to R ^18c may each be the same or different; g represents an integer from 0 to 10.

The epoxy compound (c-2-1) having at least two epoxy groups of the aforementioned formula (3-2) is prepared, for example, by adding the following formula (3-2-1) in the presence of an alkali metal hydroxide. ) structure compound is obtained by reacting with halogenated propylene oxide.

Formula (3-2-1) In Formula (3-2-1), the definitions of R ^5c to R ^18c and g are the same as the definitions of R ^5c to R ^18c and g in Formula (3-2), where No further details will be given.

Furthermore, the epoxy compound (c-2-1) having at least two epoxy groups of the aforementioned formula (3-2) is, for example, used in the presence of an acid catalyst and having the following formula (3-2-2) After the compound of the structure undergoes a condensation reaction with phenol, a compound with the structure of formula (3-2-1) is formed. Next, an excess of halogenated propylene oxide is added to perform a dehydrohalogenation reaction (dehydrohalogenation) to obtain an epoxy compound (c-2-1) having at least two epoxy groups as shown in formula (3-2) .

Formula (3-2-2) In Formula (3-2-2), R ^19c and R ^20c each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, or an aromatic group with 6 to 15 carbon atoms. group, and R ^19c and R ^20c can each be the same or different; T ¹ and T ² each independently represent a halogen atom, an alkyl group with 1 to 6 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms, and T ¹ and T ² can each be the same or different.

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

Specific examples of the above-mentioned phenols include but are not limited to: phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t- Butylphenol (t-butylphenol), octylphenol (octylphenol), nonylphenol (nonylphenol), xylenol, methylbutylphenol (methylbutylphenol), di-t-butylphenol (di-t-butylphenol), Vinylphenol, propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol, etc. The above-mentioned phenols can generally be used alone or in combination.

Based on the usage amount of the above compound having the structure of formula (3-2-2) is 1 mole, the usage amount of phenols is 0.5 mole to 20 mole, with 2 mole to 15 mole being preferred.

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 ( anhydrous aluminum chloride), zinc chloride, etc., among which p-toluenesulfonic acid, sulfuric acid or hydrochloric acid are preferred. The above-mentioned acid catalysts can be used alone or in combination.

In addition, although the usage amount of the above-mentioned acid catalyst is not particularly limited, based on the usage amount of the above-mentioned compound having the formula (3-2-2) structure is 100 weight percent (wt%), the usage amount of the acid catalyst is preferably is 0.1 wt% to 30 wt%.

The above-mentioned condensation reaction can be carried out without solvent or in the presence of organic solvent. Secondly, specific examples of the above-mentioned organic solvent include, but are not limited to, toluene, xylene, or methyl isobutyl ketone. The above-mentioned organic solvents can be used alone or in combination.

Based on the total usage amount of compounds with the structure of formula (3-2-2) and phenols being 100 wt%, the usage amount of the above-mentioned organic solvents is 50 wt% to 300 wt%, of which 100 wt% to 250 wt% is more good. In addition, the operating temperature of the above-mentioned condensation reaction is 40˚C to 180˚C, and the operating time of the condensation reaction is 1 hour to 8 hours.

After completing the above-mentioned condensation reaction, neutralization treatment or water washing treatment can be performed. The above-mentioned neutralization treatment is to adjust the pH value of the reacted solution to pH 3 to pH 7, with pH 5 to pH 7 being preferred. The above water washing treatment can be performed using a neutralizing agent, which is an alkaline substance, and specific examples thereof include: alkali metal hydroxides such as sodium hydroxide (sodium hydroxide) and potassium hydroxide (potassium hydroxide); hydrogen Calcium hydroxide, magnesium hydroxide and other alkaline earth metal hydroxides; diethylene triamine, triethylene tetramine, aniline, phenylenediamine (phenylene diamine) and other organic amines; as well as ammonia (ammonia), sodium dihydrogen phosphate (sodium dihydrogen phosphate), etc. The above-mentioned water washing treatment can be carried out by conventional methods. For example, an aqueous solution containing a neutralizing agent is added to the solution after the reaction, and extraction is performed repeatedly. After neutralization treatment or water washing treatment, heat treatment under reduced pressure, distillation of unreacted phenols and solvents, and concentration, the compound with the structure of formula (3-2-1) can be obtained.

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

In this embodiment, the alkali metal hydroxide added in the above dehydrohalogenation reaction can also use its aqueous solution. In this specific example, while the above-mentioned alkali metal hydroxide aqueous solution is continuously added to the dehydrohalogenation reaction system, water and halogenated propylene oxide can be continuously distilled out under reduced pressure or normal pressure, thereby separating and removing water. , and at the same time, halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the above-mentioned dehydrohalogenation reaction is carried out, tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl benzyl ammonium chloride, etc. can also be added. grade ammonium salt as a catalyst, and react at 50˚C to 150˚C for 1 hour to 5 hours, then add alkali metal hydroxide or its aqueous solution, and make it react at a temperature of 20˚C to 120˚C React for 1 hour to 10 hours to carry out dehydrohalogenation reaction.

Based on the total equivalent of hydroxyl groups in the above-mentioned compound having the structure of formula (3-2-1) being 1 equivalent, the usage amount of the above-mentioned halogenated propylene oxide can be from 1 to 20 equivalents, with 2 to 10 equivalents being preferred. Based on the total equivalent of hydroxyl groups in the above compound having the structure of formula (3-2-1) being 1 equivalent, the usage amount of the alkali metal hydroxide added in the above dehydrohalogenation reaction can be 0.8 equivalents to 15 equivalents, of which 0.9 is used. The equivalent to 11 equivalents is preferred.

In addition, in order to make the above dehydrohalogenation reaction proceed smoothly, in addition to alcohols such as methanol and ethanol, aprotic alcohols such as dimethyl sulfone and dimethyl sulfoxide can also be added. polar solvents, etc. to carry out the reaction. In the case of using alcohols, based on the total amount of the above-mentioned halogenated propylene oxide being 100 wt%, the usage amount of alcohols can be 2 wt% to 20 wt%, preferably 4 wt% to 15 wt%. In the example of using an aprotic polar solvent, based on the total amount of halogenated propylene oxide being 100 wt%, the usage amount of the aprotic polar solvent can be from 5 wt% to 100 wt%, where, 10 wt% It is better to reach 90 wt%.

After the dehydrohalogenation reaction is completed, water washing treatment can be optionally performed. Afterwards, halogenated propylene oxide, alcohols, aprotic polar solvents, etc. are removed by heating and reducing pressure. The above-mentioned heating and pressure reduction is performed, for example, in an environment where the temperature is 110˚C to 250˚C and the pressure is 1.3kPa (10mmHg) or less.

In order to prevent the formed epoxy resin from containing hydrolyzable halogens, solvents such as toluene and methyl isobutyl ketone can be added to the solution after the dehydrohalogenation reaction, and alkalis such as sodium hydroxide and potassium hydroxide can be added. The metal hydroxide aqueous solution is subjected to the dehydrohalogenation reaction again. In the dehydrohalogenation reaction, based on the total equivalent of hydroxyl groups in the above-mentioned compound having the structure of formula (3-2-1) being 1 equivalent, the usage amount of alkali metal hydroxide is 0.01 mole to 0.3 mole, where, 0.05 mol to 0.2 mol is preferred. In addition, the operating temperature of the above dehydrohalogenation reaction ranges from 50˚C to 120˚C, and the operating time ranges from 0.5 hours to 2 hours.

After the dehydrohalogenation reaction is completed, salts are removed through steps such as filtration and water washing. In addition, solvents such as toluene and methyl isobutyl ketone can also be distilled off by heating and reducing pressure to obtain an epoxy compound having at least two epoxy groups as shown in formula (3-2) (c-2-1). The epoxy compound (c-2-1) with at least two epoxy groups of the above formula (3-2) may include, but is not limited to, products with trade names such as NC-3000, NC-3000H, NC-3000S and NC-3000P. Products manufactured by Nippon Kayaku Co. Ltd.

The aforementioned 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 the following (1) to (3): (1) acrylic acid, methanol acrylic acid, 2-methacryloyloxyethylbutanedioic acid (2-methacryloyloxyethylbutanedioic acid), 2-methacryloyloxybutanedioic acid, 2-methacryloyloxyethyladipic acid, 2- Methacryloxybutyladipic acid, 2-methacryloxyethylhexahydrophthalic acid, 2-methacryloxyethylmaleic acid, 2-methacryloxypropylmaline Leic acid, 2-methacryloxybutyl maleic acid, 2-methacryloxypropylsuccinic acid, 2-methacryloxypropyladipic acid, 2-methacryloxypropyl tetrahydrophthalic acid, 2-methacryloxypropyl phthalic acid, 2-methacryloxybutyl phthalic acid, or 2-methacryloxybutylhydrophthalic acid Formic acid; (2) Compounds obtained by the reaction of hydroxyl-containing (meth)acrylate and dicarboxylic acid compounds, where the dicarboxylic acid compounds include but are not limited to adipic acid, succinic acid, maleic acid, ortho- Phthalic acid; (3) Half-ester compound obtained by the reaction of hydroxyl-containing (meth)acrylate and carboxylic anhydride 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-hydroxypropylmethyl Acrylate ((2-hydroxypropyl) methacrylate), 4-hydroxybutyl acrylate ((4-hydroxybutyl) acrylate), 4-hydroxybutyl methacrylate ((4-hydroxybutyl) methacrylate), or pentaerythritol trimethacrylate wait. In addition, the carboxylic acid anhydride compound described here 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 therefore will not be described again.

The mixture of the above-mentioned second alkali-soluble resin (C-2) may further optionally include a carboxylic acid anhydride compound (c-2-3) and/or an epoxy group-containing compound (c-2-4). The above-mentioned carboxylic anhydride compound (c-2-3) can be selected from the group consisting of the following (1) to (2): (1) succinic anhydride (butanedioic anhydride), maleic anhydride (maleic anhydride), Itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride , methyl hexahydrophthalic anhydride, methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride, glutaric anhydride or trimethyl Dicarboxylic anhydride compounds such as anhydride (1,3-dioxoisobenzofuran-5-carboxylic anhydride); and (2) benzophenone tetracarboxylic dianhydride (BTDA), diphenyltetracarboxylic dianhydride or diphenyl Tetracarboxylic anhydride compounds such as ether tetracarboxylic dianhydride.

The above-mentioned epoxy group-containing compound (c-2-4) is, for example, selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and unsaturated group-containing glycidyl ether compounds, A group consisting of unsaturated compounds containing epoxy groups or any combination of the above. The aforementioned unsaturated group-containing glycidyl ether compounds include but are not limited to the trade names Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192 and other compounds (the above are products of Nagase Chemical Industry Co., Ltd.).

The aforementioned second alkali-soluble resin (C-2) can be composed of an epoxy compound (c-2-1) having at least two epoxy groups of formula (3-1) and at least one carboxylic acid group and at least one vinyl non-containing resin. The saturated compound (c-2-2) undergoes a polymerization reaction to form a hydroxyl-containing reaction product, and then a carboxylic acid anhydride compound (c-2-3) is added to react. Based on the total equivalent of hydroxyl groups of the above hydroxyl-containing reaction product being 1 equivalent, the equivalent of the acid anhydride group contained in the carboxylic acid anhydride compound (c-2-3) is preferably 0.4 to 1 equivalent, more preferably 0.75 to 1 equivalent. When multiple carboxylic anhydride compounds (c-2-3) are used, they may be added sequentially or simultaneously during 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, 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.

The aforementioned second alkali-soluble resin (C-2) can be composed of an epoxy compound (c-2-1) having at least two epoxy groups of the formula (3-2) and at least one carboxylic acid group and at least one vinyl non-containing resin. The saturated group compound (c-2-2) reacts to form a hydroxyl group-containing reaction product, and then, by adding the carboxylic acid anhydride compound (c-2-3) and/or the epoxy group-containing compound (c-2 -4) Produced by polymerization reaction. The total equivalent of epoxy groups based on the epoxy compound (c-2-1) with at least two epoxy groups of formula (3-2), which has at least one carboxylic acid group and at least one ethylenic non-containing group, is 1 equivalent. The acid value equivalent of the saturated compound (c-2-2) is preferably 0.8 to 1.5 equivalents, more preferably 0.9 to 1.1 equivalents. Based on the total amount of hydroxyl groups in the above hydroxyl-containing reaction product being 100 mole %, the usage amount of the carboxylic anhydride compound (c-2-3) is preferably 10 mole % to 100 mole %, more preferably It is 20 mol% to 100 mol%, especially preferably 30 mol% to 100 mol%.

When preparing the above-mentioned 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 above reaction catalysts can be used alone or in mixture, and the above reaction catalysts include but are not limited to: triphenyl phosphine, triphenyl antimony (triphenyl stibine), triethylamine, triethanolamine (triethanolamine) , tetramethyl ammonium chloride, benzyltriethyl ammonium chloride, etc. Based on the total usage amount of the above-mentioned 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, it is 100 Parts by weight, the usage amount of the reaction catalyst is preferably 0.01 to 10 parts by weight, more preferably 0.3 to 5 parts by weight.

In addition, in order to control the degree of polymerization, a polymerization inhibitor (polymerization inhibitor) is usually added to the reaction solution. The above-mentioned polymerization inhibitors may include, but are not limited to: methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol (2,6-di -t-butyl-p-cresol) or phenothiazine (phenothiazine), etc. Generally speaking, the above-mentioned polymerization inhibitors can be used alone or in combination of multiple types. Based on the total usage amount of the above-mentioned 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, it is 100 Parts by weight, the usage amount of the polymerization inhibitor is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight.

When preparing the second alkali-soluble resin (C-2), a polymerization reaction solvent may be used if necessary. Specific examples of the polymerization reaction solvent include alcohol compounds such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; methyl ethyl ketone or cyclohexanone ketone compounds; aromatic hydrocarbon compounds such as toluene or xylene; cellosol compounds such as cellosolve or butyl cellosolve; carbitol or butyl cellosolve Carbitol compounds such as butyl carbitol; propylene glycol alkyl ether compounds such as propylene glycol monomethyl ether; polypropylene glycol alkyl ethers such as di(propylene glycol) methyl ether (poly(propylene glycol) alkyl ether) compounds; acetates such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate Compounds; alkyl lactate compounds such as ethyl 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 second alkali-soluble resin (C-2) is preferably 50 mgKOH/g to 200 mgKOH/g, more preferably 60 mgKOH/g to 150 mgKOH/g.

In addition, the polystyrene-equivalent number average molecular weight of the second alkali-soluble resin (C-2) measured by colloidal permeation chromatography is 500 to 10,000, preferably 800 to 8,000, more preferably 1,000 to 6,000.

The above-mentioned second alkali-soluble resin (C-2) can be used alone or in combination.

In this embodiment, the usage amount of the alkali-soluble resin (C) is 100 parts by weight, and the usage amount of the second alkali-soluble resin (C-2) is 0 to 90 parts by weight, preferably 10 to 80 parts by weight, More preferably, it is 20 to 70 parts by weight.

In this embodiment, based on the total weight of the solid content of the photosensitive colored resin composition being 100% by weight, the alkali-soluble resin (C) can be 5 to 75% by weight, preferably 8 to 70% by weight, More preferably, it is 10 to 65% by weight. Photopolymerizable compound ( D )

The photopolymerizable compound (D) in this embodiment may include an unsaturated compound having at least one ethylenically unsaturated group and an unsaturated compound having at least two ethylenically unsaturated groups.

Specific examples of the above-mentioned unsaturated compound having at least one ethylenically unsaturated group may include, but are not limited to, acrylamide, acrylomorpholine, methacrylomorpholine, acrylic acid-7-amino-3,7-dimethyl Octyl methacrylate, 7-amino-3,7-dimethyloctyl methacrylate, isobutoxymethacrylamide, isobutoxymethylmethacrylamide, isobornyloxyacrylate Ethyl ester, isobornyloxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethyldiglycol Acrylate, ethyldiglycol methacrylate, tert-octyl acrylamide, tert-octyl methacrylamide, diacetone acrylamide, diacetone methacrylamide, dimethylaminoacrylate Ester, dimethylaminomethacrylate, dodecyl acrylate, dodecyl methacrylate, dicyclopentyloxyethyl acrylate, dicyclopentyloxyethyl methacrylate, dicyclopentyl acrylate Pentenyl ester, dicyclopentenyl methacrylate, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, tetrachlorophenyl acrylate, tetrachlorophenyl methacrylate , 2-tetrachlorophenoxyethyl acrylate, 2-tetrachlorophenoxyethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, tetrabromophenyl acrylate, methacrylic acid Tetrabromophenyl ester, 2-tetrabromophenoxyethyl acrylate, 2-tetrabromophenoxyethyl methacrylate, 2-trichlorophenoxyethyl acrylate, 2-trimethacrylate Chlorophenoxyethyl, tribromophenyl acrylate, tribromophenyl methacrylate, 2-tribromophenoxyethyl acrylate, 2-tribromophenoxyethyl methacrylate, acrylic acid-2 -Hydroxyethyl ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, vinylcaprolactam, N-vinylpyrosanone, acrylic acid Phenoxyethyl ester, 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 combinations thereof. Among them, the unsaturated compound having at least one ethylenically unsaturated group can be used alone or in mixture of multiple types.

Specific examples of the above-mentioned unsaturated compound having at least two ethylenically unsaturated groups may include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentenyl diacrylate, and dimethacrylic acid. Dicyclopentenyl ester, triethylene glycol diacrylate, tetraethylene 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, trimethylolpropyl triacrylate, trimethylolpropyl trimethacrylate, ethylene oxide ( Trimethylolpropyl triacrylate modified by EO (hereinafter referred to as EO), trimethylolpropyl triacrylate modified by EO, trimethylolpropyl triacrylate modified by propylene oxide (PO) , PO modified trimethylolpropyl methacrylate, 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 trisacrylate Acrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, polyester diacrylate, polyester dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethyl acrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate Esters, caprolactone-modified dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexamethacrylate, caprolactone-modified dipentaerythritol pentaacrylate, caprolactone-modified dipentaerythritol pentaacrylate acrylate, ditrimethylolpropyl tetraacrylate, ditrimethylolpropyl tetramethacrylate, EO modified bisphenol A diacrylate, EO modified bisphenol A dimethacrylate, PO modified bisphenol A diacrylate, PO modified bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A diacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A dimethacrylate, PO modified tripropionate, EO modified bisphenol F diacrylate, EO modified Bisphenol F dimethacrylate, phenolic polyglycidyl ether acrylate, phenolic polyglycidyl ether methacrylate, products with model number TO-1382 manufactured by Toa Gosei Co., Ltd., or manufactured by Nippon Kayaku Co., Ltd. Products manufactured by the company and whose model number is KAYARAD DPCA-12, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120, etc. Wherein, the unsaturated compound having at least two ethylenically unsaturated groups can be used alone or in combination.

Preferred specific examples of the photopolymerizable compound (D) include trimethylolpropyl triacrylate, EO-modified trimethylolpropyl trimethacrylate, and EO-modified trimethylolpropyl triacrylate. ester, PO modified trimethylolpropyl acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified diacrylate Pentaerythritol hexaacrylate, ditrimethylolpropyl tetraacrylate, PO modified tripropionate, KAYARAD DPCA-12, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120, or combination thereof.

More preferred examples of the photopolymerizable compound (D) are dipentaerythritol hexaacrylate, dipentaerythritol tetraacrylate, EO-modified trimethylolpropyl methacrylate, or a combination thereof.

The said photopolymerizable compound (D) can be used individually or in mixture of multiple types.

Based on 100 parts by weight of the alkali-soluble resin (C), the photopolymerizable compound (D) can be 30 to 450 parts by weight, preferably 35 to 400 parts by weight, more preferably 40 to 350 parts by weight. .

In this embodiment, based on the total weight of the solid content of the photosensitive colored resin composition being 100% by weight, the photopolymerizable compound (D) may be 10% to 60% by weight, preferably 13% to 55% by weight. % by weight, more preferably 15% by weight to 50% by weight. Photoinitiator ( E )

The photoinitiator (E) in this embodiment may be a free radical photoinitiator.

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

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

The diimidazole compound is selected from 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole (2,2'-bis(o-chlorophenyl)- 4,4',5,5'-tetraphenyl-biimidazole), 2,2'-bis(o-fluorophenyl)-4,4,5,5'-tetraphenylbiimidazole (2,2'-bis (o-fluorophenyl)-4,4',5,5'-tetraphenyl-biimidazole), 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbis Imidazole (2,2'-bis(o-methyl phenyl)-4,4',5,5'-tetraphenyl-biimidazole), 2,2'-bis(o-methoxyphenyl)-4,4' ,5,5'-tetraphenyldiimidazole (2,2'-bis(o-methoxyphenyl)-4,4',5,5'- tetraphenyl-biimidazole), 2,2'-bis(o-ethyl) Phenyl)-4,4',5,5'-tetraphenylbiimidazole (2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyl-biimidazole), 2,2 '-Bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole (2,2'-bis(p-methoxyphenyl)-4,4',5,5'- tetraphenyl-biimidazole), 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole (2,2' -bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole), 2,2'-bis(2-chlorophenyl)-4,4', 5,5'-tetraphenylbiimidazole (2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole), 2,2'-bis(2,4-di Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (2,2'-bis(2,4- dichlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole), or combination thereof.

The oxime compound is selected from ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9hydro-carbazole-3-substituent]-, 1-(oxygen -Ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime), such as Ciba Specialty A product named CGI-242 manufactured by Chemicals Co., Ltd., its structure is shown in the following formula (4-1)), 1-[4-(phenylthio)phenyl]-octane-1,2-di Ketone 2-(O-benzoyloxime) (1-[4-(benzoyl)phenyl]-heptane-1,2- dione 2-(O-benzoyloxime), for example, manufactured by Ciba Specialty Chemicals The product name is CGI-124, its structure is shown in the following formula (4-2)), ethanone, 1-[9-ethyl-6-(2-chloro-4-phenylmethyl-sulfide) Ethanone, 1-[9-ethyl-6-(2-cholro-4-benzyl -thio-benzoyl)- 9H-carbazole-3-yl]-,1-(O-acetyl oxime), for example, manufactured by Asahi Denka Co., Ltd., its structure is shown in the following formula (4-3)), or a combination thereof.

Formula (4-1)

Formula (4-2)

Formula (4-3)

In one embodiment, the photoinitiator (E) may further include thioxanthone, 2,4-diethyl-thioxanthanone, thioxanthone-4-terethanone (thioxanthone-4-sulfone), benzophenone, 4,4'-bis(dimethylamino) benzophenone, 4,4'-bis(dimethylamino) benzophenone Benzophenone compounds such as (diethylamine) benzophenone (4,4'-bis(diethylamino) benzophenone); α-alpha compounds such as benzil and acetyl α-diketone compounds; acyloin compounds such as benzoin; benzoin methylether, benzoin ethylether, diphenyl acyloin ether compounds such as benzoin isopropyl ether; 2,4,6-trimethyl-benzoyl- diphenyl-phosphineoxide), bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethylphenylphosphineoxide (bis-(2,6-dimethoxy- benzoyl)-2,4 acylphosphineoxide compounds such as ,4-trimethyl-benzyl-phosphineoxide); quinone compounds such as anthraquinone and 1,4-naphthoquinone; benzene Halides such as phenacyl chloride, tribromomethyl-phenylsulfone, tris(trichloromethyl)-s-triazine, etc.; -Peroxides such as di-tertbutylperoxide. Among them, benzophenone compounds are preferred, especially 4,4’-bis(diethylamine)benzophenone.

The photoinitiator (E) is preferably 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-phenyl oxime) (such as Ciba Ciba Specialty Chemicals (trade name: CGI-124), 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl Diimidazole, 4,4'-bis(diethylamine)benzophenone, or combinations thereof.

The above-mentioned photoinitiator (E) can be used alone or in combination.

Based on 100 parts by weight of the alkali-soluble resin (C), the photoinitiator (E) can be 2 to 20 parts by weight, preferably 2 to 15 parts by weight, and more preferably 2 to 10 parts by weight. .

In this embodiment, based on the total weight of the solid content of the photosensitive colored resin composition being 100% by weight, the photoinitiator (E) can be 1 to 10% by weight, preferably 1 to 8% by weight. % by weight, more preferably 1 to 5% by weight. Solvent ( F )

The photosensitive colored resin composition of this embodiment is usually prepared by first dissolving the components other than the pigment (A) in the solvent (F) to prepare a liquid composition, and then adding the pigment (A) and mixing evenly. The solvent (F) needs to be selected to dissolve the alkali-soluble resin (C), the photopolymerizable compound (D), and the photoinitiator (E), and it needs to not react with these ingredients and have appropriate volatility. In addition, when adding dye (B) and/or additives (G), the solvent (F) must be selected to dissolve dye (B) and/or additives (G), and must not react with these ingredients and have appropriate volatility. By.

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 again. The solvents can be used alone or in combination. The solvent (F) preferably includes propylene glycol methyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, or combinations thereof.

Based on 100 parts by weight of the alkali-soluble resin (C), the solvent (F) can be 500 to 5000 parts by weight, preferably 800 to 4500 parts by weight, and more preferably 1000 to 4000 parts by weight. Additive ( G )

In this embodiment, the photosensitive colored resin composition also includes additives (G), such as fillers, polymer compounds other than the alkali-soluble resin (C), adhesion accelerators, antioxidants, ultraviolet absorbers, and anti-aggregation agents. Agents, etc.

Examples of fillers include glass, aluminum, or combinations thereof.

Examples of polymer compounds include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, or combinations thereof.

Examples of the adhesion accelerator include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, and N-(2-aminoethyl)-3-amino Propylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-epoxypropanol Propyltrimethoxysilane, 3-epoxypropylpropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane Methoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, or combinations thereof.

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

Examples of ultraviolet absorbers include 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxyphenone, or combinations thereof.

Examples of the anti-aggregation agent include sodium polyacrylate.

The above-mentioned additives (G) can be used alone or in mixture.

The above-mentioned additive (G) is preferably 3-mercaptopropyltrimethoxysilane, 2,2-thiobis(4-methyl-6-tert-butylphenol), or a combination thereof.

Based on 100 parts by weight of the alkali-soluble resin (C), the additive (G) can be 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. < Preparation method of photosensitive colored resin composition >

The method for preparing 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, add the pigment (A) to the solvent (F) to prepare a pigment dispersion, and then add an alkali to the pigment dispersion. Method of mixing soluble resin (C), photopolymerizable compound (D), photoinitiator (E), and optional additives (G); (2) put the pigment into the solvent (F) at the same time (A), alkali-soluble resin (C), photopolymerizable compound (D), photoinitiator (E), and optional additives (G) are mixed together; (3) First, add the solvent ( F), add alkali-soluble resin (C), photopolymerizable compound (D), photoinitiator (E), and optional additives (G) and mix them, then add pigment (A) and dispersion method; and (4) First, add the pigment (A) and part of the alkali-soluble resin (C) to the solvent (F) to prepare a pigment dispersion, and then add another part of the pigment dispersion to the pigment dispersion. A method of mixing an alkali-soluble resin (C), a photopolymerizable compound (D), a photoinitiator (E), and optional additives (G), etc.

It should be noted that in the above examples, the method of dispersing the pigment (A) is listed. When using the dye (B), due to the high solvent solubility of the dye (B), the dye (B) can be pre-dispersed. The preparation process of dissolving in solvent (F); or the preparation process of dissolving dye (B) and other ingredients in solvent (F) at the same time.

Among these methods, the above-mentioned methods (1) and (4) are preferred from the viewpoint of effectively preventing pigment aggregation and uniformly dispersing the pigment.

Examples of methods for uniformly dispersing/mixing each component include mixing and/or dispersing using a stirrer and/or disperser. Examples of dispersing machines include roller mills such as two-roller mills and three-roller mills, ball mills such as ball mills and vibrating ball mills, paint conditioners, continuous disc-type bead mills, and continuous ring-type bead mills. The optimal dispersion conditions of the bead mill are: 0.03mm~2.00mm, and more preferably 0.10mm~1.0mm.

The present invention will be further described with the following experimental examples, but it should be understood that these experimental examples are only for illustration and should not be interpreted as limitations on the implementation of the present invention. Synthesis example of alkali-soluble resin ( C ) Synthesis example C-1-1

Mix 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, and 35 parts by weight of benzene methacrylate. Methyl ester and 30 parts by weight of nitrogen-phenylmaleimide are placed in a round-bottomed flask equipped with a stirrer and a condenser, and the inside of the flask is filled with nitrogen. Afterwards, stir slowly and raise the temperature to 80°C. The reactants were mixed uniformly and polymerization was carried out for 4 hours. After that, the temperature is raised to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile is added and polymerized for 1 hour to obtain the first alkali-soluble resin of Synthesis Example C-1-1. Synthesis example C-1-2

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 methane Benzyl acrylate is placed in a round-bottomed flask equipped with a stirrer and a condenser, and the inside of the flask is filled with nitrogen. Afterwards, stir slowly and raise the temperature to 80°C to evenly mix the reactants and proceed with the polymerization reaction 3 hours. After that, the temperature is raised to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile is added and polymerized for 1 hour to obtain the first alkali-soluble resin of Synthesis Example C-1-2. Synthesis example C-1-3

Mix 2 parts by weight of 2,2'-azobisisobutyronitrile, 300 parts by weight of dipropylene glycol methyl ether, 20 parts by weight of 2-methacryloyl ethoxysuccinate, and 15 parts by weight of acrylic acid bicyclo Pentenyl ethyl oxide and 65 parts by weight of benzyl methacrylate were placed in a round-bottomed flask equipped with a stirrer and a condenser, and the inside of the flask was filled with nitrogen. After that, the temperature was slowly stirred and heated to 80°C. , the reactants were mixed evenly and the polymerization reaction was carried out for 3 hours. After that, the temperature is raised to 100°C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile is added to polymerize for 1 hour. The first alkali-soluble resin of Synthesis Example C-1-3 can be obtained. Experimental Examples 1 to 11 and Comparative Examples 1 to 4

Experimental Examples 1 to 11 and Comparative Examples 1 to 4 of the photosensitive colored resin composition will be described below: Experimental Example 1 a. Preparation of the photosensitive colored resin composition

First, put 1.0 parts by weight of pigment (A-1-1) (ie, compound (1-1)) and Ajisper PB821 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) into a 30 ml jar. (As a dispersant) 0.6 parts by weight of propylene glycol methyl ether acetate (PGMEA for short, manufactured by Daicel-Allnex) 8.4 parts by weight of zirconia beads with a particle size of 2 mm 2.0 parts by weight, after preparatory grinding for 1 hour using a paint shaker (PCMH-C50M, manufactured by Asada Steel), transfer the solution to another 30 ml wide-mouth bottle, and add 2.0 mass of zirconia beads with a particle size of 0.1 mm. parts, and vibrated with a paint shaker for 20 hours to obtain the pigment dispersion of Experimental Example 1.

Next, 10 parts by weight of the above-mentioned pigment dispersion (which contains 1.0 parts by weight of pigment (A-1-1)) and 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-Benzyl oxime) (trade name OXE-01, manufactured by BASF) (hereinafter referred to as E-1) was added with 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) in a mixed solvent and stirred evenly with a shaking type stirrer to prepare Experimental Example 1. Photosensitive colored resin composition. b. Production of patterns (which can be used as colored layers of color filters)

The photosensitive colored resin composition of Experimental Example 1 was coated on a 100mm×100mm glass substrate by spin coating. It was first dried under reduced pressure at a pressure of 100mmHg for 30 seconds, and then prebaked at a temperature of 100mmHg. 90℃, 2 minutes, a pre-baked coating film with a film thickness of 1.2 μm can be formed, and then the pre-baked coating film is irradiated with ultraviolet light (exposure machine Canon PLA-501F) with a light intensity of 100mJ/cm ² Then, immerse it in the developer at 23°C for 1 minute, wash it with pure water, and bake it at 200°C for 1 minute to form a pattern with a film thickness of 1.0 μm on the glass substrate (which can be used as a color filter). shading layer).

The obtained pattern of Experimental Example 1 was evaluated by the evaluation method described below, and the results are shown in Table 1. Experimental Example 2 to Experimental Example 11 , Comparative Example 1 to Comparative Example 4

The photosensitive colored resin compositions and colored layers (color filters) of Experimental Examples 2 to 21 and Comparative Examples 1 to 4 were prepared by the same steps as Experimental Example 1, and the differences are that : Change the component type and usage amount of the photosensitive colored resin composition, as well as the temperature and time of the post-baking process. Among them, Experimental Examples 2 to 21 are shown in Table 1, and Comparative Examples 1 to 4 are shown in Table 2). The ingredients corresponding to the numbers in Table 1 and Table 2 are shown in Table 3. The obtained photosensitive colored resin composition was evaluated in the following evaluation method. The results of Experimental Examples 2 to 21 and Comparative Examples 1 to 4 are shown in Table 1 and Table 2, respectively.

Table 1 Ingredients (parts by weight) Experimental example 1 2 3 4 5 6 7 8 9 10 11 Pigments (A) A-1 A-1-1 1 A-1-2 10 A-1-3 50 A-1-4 A-1-5 100 A-1-6 150 A-1-7 A-1-8 10 40 A-1-9 20 50 A-1-10 30 80 A-2 A-2-1 10 A-2-2 Dye(B) B-1 B-1-1 1 B-1-2 30 B-1-3 B-1-4 50 B-2 B-2-1 1 B-2-2 10 Alkali-soluble resin (C) C-1 C-1-1 100 100 100 100 C-1-2 100 100 50 100 100 C-1-3 100 50 100 Photopolymerizable compound (D) D-1 30 100 200 400 D-2 50 150 250 350 D-3 50 150 300 Photoinitiator (E) E-1 2 5 5 10 E-2 5 5 8 15 E-3 5 3 3 10 Solvent (F) F-1 460 300 500 100 200 300 400 500 800 1000 1500 F-2 40 900 1200 2000 2500 F-3 200 1300 1600 2200 2500 Additive (G) G-1 1 G-2 Post-bake temperature (℃) 200 230 250 200 230 250 200 230 250 200 230 Post-baking time (minutes) 1 12 15 3 8 10 1 12 15 3 8 Evaluation results Post-baking residual film rate ○ ○ ○ ○ ○ ○ ○ ○ ○ ◎ ◎

Table 1 (continued) Ingredients (parts by weight) Experimental example 12 13 14 15 16 17 18 19 20 twenty one Pigments (A) A-1 A-1-1 250 A-1-2 250 A-1-3 50 A-1-4 300 A-1-5 200 A-1-6 250 A-1-7 200 300 A-1-8 250 A-1-9 200 A-1-10 100 A-2 A-2-1 A-2-2 50 Dye(B) B-1 B-1-1 50 50 80 B-1-2 60 40 90 B-1-3 60 30 B-1-4 80 50 B-2 B-2-1 B-2-2 Alkali-soluble resin (C) C-1 C-1-1 100 100 100 C-1-2 100 100 100 C-1-3 100 100 100 100 Photopolymerizable compound (D) D-1 400 50 200 D-2 300 350 400 150 300 D-3 250 400 450 Photoinitiator (E) E-1 8 15 10 E-2 10 5 18 15 E-3 10 10 5 20 Solvent (F) F-1 2000 2500 3000 3000 2500 2000 1000 2000 2500 5000 F-2 1000 500 2000 500 F-3 1000 2500 500 Additive (G) G-1 G-2 0.5 Post-bake temperature (℃) 250 200 230 250 200 230 250 250 230 200 Post-baking time (minutes) 10 1 12 15 3 8 10 3 8 10 Evaluation results Post-baking residual film rate ◎ ◎ ◎ ◎ ◎ ◎ ◎ ※ ※ ※

Table 2 Ingredients (parts by weight) Comparative example 1 2 3 4 Pigments (A) A-1 A-1-1 250 A-1-2 A-1-3 A-1-4 A-1-5 200 A-1-6 A-1-7 A-1-8 A-1-9 A-1-10 A-2 A-2-1 A-2-2 50 Pigments (A') A'-1-1 50 A'-1-2 100 Dye(B) B-1 B-1-1 B-1-2 60 B-1-3 B-1-4 50 B-2 B-2-1 B-2-2 Alkali-soluble resin (C) C-1 C-1-1 100 100 100 C-1-2 C-1-3 100 Photopolymerizable compound (D) D-1 200 D-2 350 D-3 50 250 Photoinitiator (E) E-1 10 8 10 E-2 E-3 5 Solvent (F) F-1 500 1000 2500 2000 F-2 2500 F-3 Additive (G) G-1 G-2 0.5 Post-bake temperature (℃) 250 200 200 250 Post-baking time (minutes) 15 3 17 25 Evaluation results Post-baking residual film rate ╳ ╳ ╳ ╳

table 3 abbreviation Element A-1-1 Compound (1-1) A-1-2 Compound (1-2) A-1-3 Compounds (1-3) A-1-4 Compounds (1-4) A-1-5 Compounds (1-6) A-1-6 Compounds (1-7) A-1-7 Compounds (1-17) A-1-8 Compounds (1-10) A-1-9 Compounds (1-11) A-1-10 Compound (1-14)) A'-1-1 A'-1-2 A-2-1 CI Pigment Blue 15:4 A-2-2 CI Pigment Blue 15:6 B-1-1 The compound represented by formula (i-1), wherein R ^c and R ^d each independently represent -SO ₃ -; n represents 0. B-1-2 Compounds represented by formula (i-22) B-1-3 Compounds represented by formula (i-28) B-1-4 Compounds represented by formula (i-31) B-2-1 CI acid red 37 B-2-2 CI acid blue 29 C-1-1 The first alkali-soluble resin of Synthesis Example C-1-1 C-1-2 The first alkali-soluble resin of Synthesis Example C-1-2 C-1-3 The first alkali-soluble resin of Synthesis Example C-1-3 D-1 Dipentaerythritol hexaacrylate (DPHA) D-2 Dipentaerythritol tetracrylate D-3 EO modified trimethylolpropyl methacrylate E-1 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-phenyl oxime) (1-[4-(benzoyl)phenyl]-heptane-1, 2- dione 2-(O-benzoyloxime), such as CGI-124 manufactured by Ciba Specialty Chemicals) E-2 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole (2,2'-bis(2,4-dichlorophenyl)-4,4 ',5,5'-tetraphenyl-biimidazole) E-3 4,4'-bis(diethylamino)benzophenone F-1 Propylene glycol methyl ether acetate (PGMEA for short) F-2 Ethyl 3-ethoxypropionate F-3 cyclohexanone G-1 3-Thiopropyltrimethoxysilane G-2 2,2-Thiobis(4-methyl-6-tert-butylphenol) [ Evaluation method ] Post-baking residual film rate

For the formed pattern, the film thickness before and after post-baking was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and the post-baking residual film rate was calculated according to the following formula. The results are shown in Table 1 and Table 2. Post-baking residual film rate (%) = (film thickness after post-baking/film thickness before post-baking) × 100 (%)

A large value indicates a high and good film residual rate after post-baking. If the residual film rate is high, unfavorable situations such as cracks or haze due to film shrinkage during heating are less likely to occur. ※: The film remaining rate after baking is >98%. ◎: 98%≧Remnant film rate after baking＞95%. ○: 95%≧Remnant film rate after baking＞93%. △: 93%≧Remnant film rate after baking>90%. ╳: Post-baking residual film rate ≦90%. ＜ Evaluation results ＞

It can be seen from Table 1 and Table 2 that compared with the colored layers produced by post-baking time of not 1 minute to 15 minutes and/or the photosensitive colored resin composition not containing pigment (A-1) (Comparative Examples 1 to 4 ), under the conditions that the temperature of the post-baking treatment is 200°C to 250°C, the post-baking time is 1 minute to 15 minutes, and the photosensitive colored resin composition contains the pigment (A-1) (Experimental Examples 1 to 21 ), the pattern (colored layer) produced by the photosensitive colored resin composition has a good post-baking residual film rate.

Among them, when the post-baking time is longer 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.

In addition, when the photosensitive colored resin composition does not contain the pigment (A-1) (Comparative Examples 1 and 2), the post-baking residual film rate of the pattern produced by the photosensitive colored resin composition is not good.

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

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

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

In summary, the present invention provides a method for manufacturing a color filter, which uses a photosensitive colored resin composition that contains a compound represented by formula (1) as a pigment (A-1) and is post-baked. Under the condition of a temperature of 200℃~250℃, the pattern is post-baked for 1 minute to 15 minutes, so that the colored layer (pattern) in the color filter has a good post-baking residual film rate, thereby avoiding color mixing. , pattern dissolution and other problems; at the same time, the coloring layer (pattern) can also be produced with a relatively small amount of photosensitive coloring resin composition, thereby achieving the effect of saving resources and being environmentally friendly.

Although the present invention has been disclosed above through embodiments, they are not intended to limit the present invention. Anyone with ordinary knowledge in the technical field may make some modifications and modifications without departing from the spirit and scope of the present invention. Therefore, The protection scope of the present invention shall be determined by the appended patent application scope.

without

without

Claims (10)

A method for manufacturing a color filter, including: applying a photosensitive colored resin composition on a substrate to obtain a coating film; exposing the coating film through a photomask; using a developer to The coating film is developed to obtain a pattern; and the pattern is post-baked for 1 minute to 15 minutes in a temperature range of 200°C to 250°C, wherein the photosensitive colored resin composition includes pigment (A) , alkali-soluble resin (C), photopolymerizable compound (D), photoinitiator (E), and solvent (F), the pigment (A) includes a pigment (A-1), wherein the pigment (A) -1) is a compound represented by formula (1), 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 at least π bonded directly to N. An aliphatic hydrocarbon group having a saturated aliphatic hydrocarbon group at the end of the knot, or an aromatic group having the aliphatic hydrocarbon group, the carbon chain of the aliphatic hydrocarbon group may contain O, S, N, and the carbon chain of the aromatic group may Contains O, S, N; B ^q- represents a heterogeneous multiple acid anion with q valence; R ¹ , R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group , where at least one of R ² , R ³ , R ⁴ , and R ⁵ is a substituted or unsubstituted alkyl group, R ² and R ³ can be bonded to each other to form a ring structure, and R ⁴ and R ⁵ can be bonded to each other. The bonds form a ring structure, and multiple R ¹ , R ² , R ³ , R ⁴ , and R ⁵ can each be the same or different; R ⁶ and R ⁷ each independently represent a substituted or unsubstituted alkyl group, Substituted or unsubstituted alkoxy group, halogen atom, or cyano group; Ar represents a substituted or unsubstituted divalent aromatic group, and multiple Ar can each be the same or different; p and q represent 2 or more Integers; r and s represent integers above 1; v represents 0 or 1. When v represents 0, there is no bond; t and u independently represent integers above 0 and below 4; t+v and u+v are An integer from 0 to 4. The manufacturing method of a color filter as described in claim 1, wherein R ² , R ³ , R ⁴ , and R ⁵ each independently represent a substituted or unsubstituted alkyl group. The manufacturing method of a color filter according to claim 1, wherein in B ^q- , the heterogeneous polyacid anion contains at least one of molybdenum and tungsten. The manufacturing method of a color filter as described in claim 1, wherein the post-baking treatment time is 3 to 10 minutes. The manufacturing method of a color filter according to claim 1, wherein the photosensitive colored resin composition further includes a dye (B), the dye (B) includes a dye (B-1), wherein the dye ( B-1) is a compound represented by formula (2), Formula (2) In Formula (2), R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ each independently represent 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 instead An aromatic hydrocarbon group with a carbon number of 6 to 10; 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 can each be the same or different; X represents a halogen atom; n represents 0 or 1; L ¹ represents the carbon number is an alkyl group with 1 to 10 carbon atoms or an alkyl group with a carbon number of 1 to 10 substituted by a halogen atom, in which the alkyl group with a carbon number of 1 to 10 or an alkyl group with a carbon number of 1 to 10 substituted with a halogen atom is -CH ₂ -Unsubstituted or substituted by -O-, carbonyl or -NL ⁴ -; L ⁴ represents an alkyl group with 1 to 10 carbon atoms or an alkyl group with 1 to 10 carbon atoms substituted by a halogen atom; L ² and L ³ each independently represent a linear alkyl group with 1 to 10 carbon atoms, a branched alkyl group with 3 to 10 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, or -Q; where, the number of carbon atoms The hydrogen atoms in the linear alkyl group with 1 to 10 carbon atoms, the branched chain alkyl group with 3 to 10 carbon atoms, or the cycloalkyl group with 3 to 30 carbon atoms are unsubstituted or substituted by a substituent. Selected from the group consisting of hydroxyl group, halogen atom, -Q, -CH=CH ₂ and -CH=CH-L ¹ ; linear alkyl group with 1 to 10 carbon atoms, branched chain with 3 to 10 carbon atoms -CH ₂ - in an alkyl group or a cycloalkyl group with 3 to 30 carbon atoms is unsubstituted or substituted with -O-, carbonyl group or -NL ⁴ -; or L ² and L ³ are bonded to each other to form a carbon number of 1 ~10 heterocyclic groups, in which the hydrogen atoms in the heterocyclic groups with 1 to 10 carbon atoms are unsubstituted or substituted by L ¹ , -OH, or -Q; Q represents an aromatic hydrocarbon group with 6 to 10 carbon atoms , a heteroaryl group with a carbon number of 5 to 10, with a carbon number of 6 substituted by a halogen atom, -L ¹ , -OH, -OL ¹ , -NO ₂ , -CH=CH ₂ or -CH=CH-L ¹ ~10 aromatic hydrocarbon groups, or heteroaromatics with 5 to 10 carbon atoms substituted by halogen atoms, -L ¹ , -OH, -OL ¹ , -NO ₂ , -CH=CH ₂ or -CH=CH-L ¹ base; M represents potassium or sodium. The manufacturing method of a color filter according to claim 1, wherein the alkali-soluble resin (C) is 100 parts by weight and the pigment (A-1) is 1 to 300 parts by weight; and based on the The total solid content of the photosensitive colored resin composition is 100% by weight, and the pigment (A-1) is 0.5% to 50% by weight. The manufacturing method of a color filter according to claim 5, wherein the dye (B) is 1 to 90 parts by weight based on 100 parts by weight of the alkali-soluble resin (C). -1) is 1 to 90 parts by weight; and the dye (B) is 0.1 to 20% by weight based on 100% by weight of the total solid content of the photosensitive colored resin composition, so The dye (B-1) is 0.1% by weight to 20% by weight. The manufacturing method of a color filter according to claim 1, wherein the alkali-soluble resin (C) is 100 parts by weight, the pigment (A) is 1 to 300 parts by weight, and the photopolymerizable The compound (D) is 30 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 The total solid content of the photosensitive colored resin composition is 100% by weight, the pigment (A) is 0.5% to 50% by weight, and the alkali-soluble resin (C) is 5% to 75% by weight, The photopolymerizable compound (D) is 10% to 60% by weight, and the photoinitiator (E) is 1% to 10% by weight. A color filter made by the color filter manufacturing method according to any one of claims 1 to 8. A liquid crystal display device including the color filter as described in claim 9.