TW202225202A - Coloring resin composition, and photoresist structure, color filter and display device using the same - Google Patents

Abstract

A coloring resin composition, and a photoresist, a color filter and a display device using the same are provided. The coloring resin composition includes a colorant, an alkali-soluble resin, a polymerizable unsaturated monomer, a photo initiator and a solvent. The alkali-soluble resin includes a photopolymerizable resin having a weight-average molecular weight (Mw) less than 20000, and the acid value determined by titrating g a potassium hydroxide (KOH) is less than 100 mg KOH/g.

Description

Colored resin composition, photoresist structure using the same, color filter and display device

The present invention relates to a composition and a photoresist structure using the same, a color filter and a display device, and particularly relates to a colored resin composition and a photoresist structure, a color filter and a display device using the same.

Display devices have been widely used in daily life, including various portable or non-portable electronic products, workplace equipment, smart home appliances, transportation, or public use, etc., to provide relevant information and/or interactive modes to enhance User convenience and fun in life and work. The photoresist plays an important role in the display device. Taking a color liquid crystal display device as an example, a color filter is used in the color liquid crystal display device to present a color display screen. Color filters include photoresist layers of different colors, and typical color filters include, for example, four colors of photoresist, red, green, blue, and black. The optical properties of the color filter have a key influence on the optical display effect of the color liquid crystal display device.

Although the current photoresist compositions are generally suitable in terms of their formation methods, they do not fully satisfy all requirements. There are still various attempts and adjustments for photoresist compositions in color filters.

Some embodiments of the present invention disclose a coloring resin composition comprising a colorant, an alkali-soluble resin, a polymerizable unsaturated compound, a photopolymerization initiator and a solvent, wherein the alkali-soluble resin comprises a photocurable resin, the photocurable resin is The weight-average molecular weight (Mw) of the resin is less than 20,000, and the potassium hydroxide (KOH) titration acid value is less than 100 mg/g.

In some embodiments, the potassium hydroxide (KOH) titration acid value of the photocurable resin is less than 55 mg/g.

In some embodiments, the weight average molecular weight of the photocurable resin is less than 10,000.

In some embodiments, the weight average molecular weight of the photocurable resin is between 6,000 and 20,000. Furthermore, the -COOH group contained in the photocurable resin, for example, accounts for less than 7 %/mol of the photocurable resin.

Some embodiments of the present invention disclose a color filter comprising a photoresist layer, the photoresist layer is formed by applying the above-mentioned colored resin composition over a substrate and exposing and developing.

Some embodiments of the present invention disclose a display device including the above-mentioned color filter. The light-transmitting layer or the light-shielding and reflecting layer is formed by applying the above-mentioned colored resin composition on a substrate and curing.

In addition to common liquid crystal displays, the mainstream of display technology development in recent years, such as organic light-emitting diode (OLED) displays, are also increasingly popular, and other new types of display technologies such as highly luminous, long-life micro-light-emitting diodes with great market prospects Bulk (Mini LED) and sub-millimeter light-emitting diode Micro LED are also attracting attention. With the development of various types of display technologies, the demand for photoresist characteristics also increases. Taking a display device including a color filter substrate as an example, a colored resin composition can be used as a photoresist material to form a color filter photoresist structure on a substrate. In general, for various types of display applications, the composition of the pigmented resin composition can be adjusted and optimized to form a variety of color filters with predetermined characteristics, including the formation of a full profile with smaller undercuts and a smaller profile. Forming a complete photoresist structure is also one of the goals that the industry is concerned about and striving for. However, the photoresist structure formed on the substrate by the current colored resin composition is still prone to have large or even deep undercuts, resulting in defects such as partial peeling or incomplete outline.

In addition, general photoresist materials may include resin materials, polymerizable unsaturated compounds, photopolymerization initiators, solvents and other additives, wherein the resin material acts as a binder and the solvent can dissolve other materials / Diluent liquid of the compound, so that the photoresist exists in liquid form for ease of use. General photoresist materials can be divided into positive photoresist and negative photoresist because of their characteristics. The positive photoresist itself is insoluble in the developing solution, but after being irradiated by light to react, it will dissociate into an acidic polymer compound that is easily soluble in the developing solution (alkaline). , but after being irradiated by light to react, new polymer bonds will be generated to strengthen the structure and be insoluble in the developer. The following description is made by taking negative photoresist as the photoresist material in some embodiments of the present disclosure.

FIG. 1A is a schematic cross-sectional view of a photoresist structure formed with a current colored resin composition. FIG. 1B is a top view of the photoresist structure formed with the current colored resin composition. In the photoresist manufacturing process, the crosslinking (Crosslink) of the bottom of the photoresist structure 11 close to the substrate 10 is insufficient because the exposure intensity decreases with the thickness of the photoresist. Furthermore, during the developing process of the photoresist, the bottom of the photoresist will have a certain undercut depth d ₀ due to the undercut effect. At present, the photoresist structure 11 made of the colored resin composition has a slightly concave top surface in cross section, and the most edge point of the photoresist structure 11 and the bottom surface 11b of the contact substrate 10 have a large undercut depth d ₀ . As shown in Figure 1A. If the undercut is too deep, photoresist peeling is likely to occur during the developing process. For example, at the circled place in Figure 1B, the profile of the long photoresist structure 11 has a missing corner, which may cause the image of the display device. The number of defects in the photoresist is too high due to the fact that the light is exposed, or the uneven light and dark lines are generated, which makes the detector misjudge the photoresist.

In order to meet the above needs, the embodiments of the present disclosure propose a colored resin composition, and a photoresist structure, a color filter, and a display device formed by using the colored resin composition. In some embodiments, the colored resin composition is coated over a substrate of a display device, and is cured by baking and photolithography processes (eg, exposure and development steps) to form a patterned photoresist layer, wherein the pattern The photoresist layer includes a plurality of photoresist structures. In some embodiments, the aforementioned photoresist structure is, for example, a convex body. The coloring resin composition proposed in the embodiment includes an alkali-soluble resin, and the one or more copolymers contained in the alkali-soluble resin can make the photoresist structure formed by the coloring resin composition after exposure and development to present a relatively intact mushroom shape. cross section, and significantly improve the problem of undercut too deep after the photoresist structure is formed by the traditional colored resin composition.

Various embodiments are provided below for detailed description. The embodiments are only used as examples to illustrate, and do not limit the scope of protection of the present disclosure. The present disclosure can still be implemented by adopting other features, elements, methods and parameters. The embodiments are provided only to illustrate the technical features of the present disclosure, and are not intended to limit the scope of the patent application of the present disclosure. Those with ordinary knowledge in the technical field can make equivalent modifications and changes according to the description of the following specification without departing from the spirit and scope of the present disclosure.

FIG. 2A is a schematic cross-sectional view of a photoresist structure formed with the colored resin composition according to some embodiments of the present disclosure. The coloring resin composition proposed in some embodiments comprises an alkali-soluble resin, and the alkali-soluble resin may contain a photo-curable resin, or a combination of a photo-curable resin and a thermosetting resin. The upper part (farther away from the substrate 20 ) and the lower part (closer to the substrate 20 ) of the photoresist layer formed on the substrate 20 by the colored resin composition of the embodiment have less difference in the degree of crosslinking, thereby reducing the crosslinking degree The difference in strength between the upper and lower parts of the rear composition. Therefore, when the colored resin composition of the embodiment is coated on the substrate 20 and undergoes an optical lithography process, the upper part and the lower part of the photoresist layer may have little difference or even similar undercut resistance, so after developing The photoresist structure 21 has a good and complete shape, and also does not have the defect that the undercut is too deep after the photoresist structure is formed by the conventional colored resin composition.

In some embodiments, as shown in FIG. 2A , the photoresist structures 21 on the substrate 20 are convex bodies. For example, the photoresist structure 21 has a mushroom-shaped cross-section, that is, the top of the photoresist structure 21 is larger and the lower part is slightly retracted. In some embodiments, a vertical projected area of the convex photoresist structure 21 on the substrate 20 is larger than the contact area between the bottom surface 21 b of the photoresist structure 21 and the substrate 20 . As shown in FIG. 2A , the photoresist structure 21 has a vertical projection area A ₁ on the substrate 20 , and a contact area A 2 is formed between the bottom surface 21 b of the photoresist structure 21 and the substrate 20 , wherein the vertical projection area A ₁ has a contact area A ₂ . The area is greater _than the area of the contact area A2. According to the colored resin composition proposed by some embodiments of the present application, the area of the contact area A2 of the formed photoresist structure ₂₁ can be at least in the range of 94%-100% _of the area of the vertical projection area A1.

In some embodiments, as shown in FIG. 2A , the top of the photoresist structure 21 which is a convex body has an arc. Furthermore, in some embodiments, the cross-section of the photoresist structure 21 also includes an arc-shaped line segment from the top to the side edges. For example, a parallel line L1 is drawn parallel to the substrate 20 at a highest vertex of the convex body (for example, the point a indicated in FIG. 2A ), and a parallel line L1 is drawn at the most distal point of the edge of the convex body (for example, as shown in FIG. 2A ). The marked point b) draws a vertical line L2 perpendicular to the substrate 20, wherein the parallel line L1 and the vertical line L2 form an included angle equal to 90 degrees, and the cross-section of the convex body (for example, along the XZ plane) is at the parallel line L1 An arc line segment 21c is included between the vertical line L2 and the vertical line L2.

Furthermore, in some embodiments, as shown in FIG. 2A , the photoresist structure 21 is perpendicular to a cross-section of the substrate 20 (eg, along the XZ plane) at an edge point (eg, point b marked in FIG. 2A ) There is a gap _UC between the position where the bottom surface 21b of the convex body contacts with the substrate 20 . The notch _UC may also be referred to as an undercut, and the depth of the notch _UC along, for example, the X-direction may also be referred to as an undercut depth d.

In other words, as shown in FIG. 2A , the vertical projection of the farthest point of one of the edges of the photoresist structure 21 (for example, point b marked in FIG. 2A ) on the substrate 20 and the bottom surface of the photoresist structure 21 The position where 21b contacts the substrate 20 (eg, point c marked in FIG. 2A ) has a distance in the X direction, for example, which is defined as the undercut depth d of the photoresist structure 21 .

According to the colored resin composition proposed by some embodiments of the present application, the undercut depth d of the photoresist structure 21 formed may be less than about 1 μm. Therefore, compared with the photoresist structure 11 shown in FIG. 1A , the photoresist structure 21 (as shown in FIG. 2A ) formed on the substrate 20 with the colored resin composition proposed in the embodiment can effectively improve the The undercut depth of the traditional photoresist material after the photoresist structure is formed is too deep.

FIG. 2B is a top view of a photoresist structure formed with the colored resin composition according to some embodiments of the present disclosure. Please refer to both Figure 1B and Figure 2B. Compared with the strip-shaped photoresist structure 11 shown in FIG. 1B , a plurality of strip-shaped photoresist structures 21 (as shown in FIG. 2B ) are formed on the substrate 20 with the colored resin composition of the embodiment. ), can present a complete profile without undercutting too deep, or local peeling (peeling) defects, or uneven light and dark lines, which makes the detector misjudge the number of photoresist defects is too high, affecting the process.

Some embodiments of the present disclosure relate to a colored resin composition and applications thereof, including a photoresist structure formed using the colored resin composition, a color filter including the photoresist structure, and a display device including the color filter . In some embodiments, the colored resin composition includes a colorant, an alkali-soluble resin, a polymerizable unsaturated compound, a photopolymerization initiator, and a solvent, wherein the alkali-soluble resin includes a photocurable resin, and the weight of the photocurable resin is The average molecular weight (Mw) is less than 20,000, and the potassium hydroxide (KOH) titration acid value is less than 100 mg KOH/g. The colored resin composition of the embodiment has good resistance to side etching, and can improve the problem of peeling off or uneven light and dark lines caused by the formed photoresist structure during the development process. In some embodiments, the alkali-soluble resin may comprise one or more photosetting resins, one or more thermosetting resins, or a combination of the foregoing resins.

In some embodiments, taking the total weight of the colored resin composition as 100 wt %, the colorant accounts for about 10 wt % to about 30 wt % of the colored resin composition; the alkali-soluble resin accounts for the coloring about 5% to about 50% by weight of the resin composition; the polymerizable unsaturated compound accounts for about 5% to about 50% by weight of the colored resin composition; the photopolymerization initiator accounts for all the about 0.1 wt % to about 10 wt % of the colored resin composition. In some embodiments, the alkali-soluble resin is a binder, which enables the colored resin composition to be smoothly attached to the surface of the substrate, and effectively provides resistance against corrosion by acid, alkali or plasma.

In some embodiments, the colorant of the colored resin composition may include pigments and dyes. The pigment of the colorant is not particularly limited, and known pigments can be used, and examples thereof include compounds classified as pigments in the color index (published by The Society of Dyers and Colourists). According to some embodiments, the dye of the colorant is not particularly limited, as long as it can be appropriately selected in accordance with the desired spectral spectrum of the color filter.

In some embodiments, the colorants include green pigments and/or yellow pigments and/or blue pigments

In some embodiments, the pigment of the colorant refers to a dispersion comprising green pigment and/or yellow pigment and/or blue pigment. In the embodiment, the dispersion liquid of green pigment and/or yellow pigment and/or blue pigment comprises a mixture of propylene pigment dispersant, pigment dispersing resin and propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate) through a bead mill. prepared by dispersion.

In some embodiments, as green pigments in the coloring agent of the present invention, phthalocyanine pigments, methanimine metal complex pigments, etc. can be cited. Specifically, for example, C.I. Pigment Green 1, C.I. Pigment Green 4, C.I. Pigment Green 4, C.I. Pigment Green 7, C.I. Pigment Green 8, C.I. Pigment Green 36, C.I. Pigment Green 58, etc. In one embodiment, the colorant of the present invention may include a halogenated metal phthalocyanine pigment as a pigment. Halogenated metal phthalocyanine pigments include halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments, and it is particularly preferable to contain halogenated zinc phthalocyanine pigments such as C.I. Pigment Green 58 and C.I. Pigment Green 59. In the present invention, C.I. Pigment Green 58 is particularly preferred.

In some embodiments, the colorants of the present invention may include yellow pigments, such as monoazo pigments, monoazo lake pigments, disazo pigments, anthraquinone pigments anthraquinone pigment, monoazo pyrazolone pigment, condensed azo pigment, isoindoline pigment, benzimidazolone pigment, formazan Imine metal complex pigment (azomethine metal complex pigment), quinophthalone pigment (quinophthalone pigment), quinoxaline pigment (quinoxaline pigment) etc. Specifically, for example, can be used: C.I. Pigment Yellow 1, C.I. Pigment Yellow 2 , C.I. Pigment Yellow 3, C.I. Pigment Yellow 4, C.I. Pigment Yellow 5, C.I. Pigment Yellow 6, C.I. Pigment Yellow 10, C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. , C.I. Pigment Yellow 17, C.I. Pigment Yellow 18, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 32, C.I. Pigment Yellow 34, C.I. Pigment Yellow 35, C.I. Pigment Yellow 36, C.I. Pigment Yellow 36:1, C.I. Pigment Yellow 37, C.I. Pigment Yellow 37:1, C.I. Pigment Yellow 40, C.I. Pigment Yellow 42, C.I. Pigment Yellow 43, C.I. Pigment Yellow 53, C.I. Pigment Yellow 55, C.I. Pigment Yellow 60, C.I. Pigment Yellow 61, C.I. Pigment Yellow 62, C.I. Pigment Yellow 63, C.I. Pigment Yellow 65, C.I. Pigment Yellow 73, C.I. Pigment Yellow 74, C.I. Pigment Yellow 77, C.I. Pigment Yellow 81, C.I. Pigment Yellow 83, C.I. Pigment Yellow 86. C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 95, C.I. Pigment Yellow 97, C.I. Pigment Yellow 98, C.I. Pigment Yellow 100, C.I. Pigment Yellow 101, C.I. Pigment Yellow 104, C.I. Pigment Yellow 106, C.I. Pigment Yellow 108, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 113, C.I. Pigment Yellow 114, C.I. Pigment Yellow 115, C.I. Pigment Yellow 116, C.I. Pigment Yellow 117, C.I. Pigment Yellow 118, C.I. Pigment Yellow 119, C.I. 120. C.I. Pigment Yellow 123, C.I. Pigment Yellow 125, C.I. Pigment Yellow 126, C.I. Pigment Yellow 127, C.I. Pigment Yellow 128, C.I. Pigment Yellow 129, C.I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. C.I. Pigment Yellow 148, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 152, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 156, C.I. C.I. Pigment Yellow 164, C.I. Pigment Yellow 166, C.I. Pigment Yellow 167, C.I. Pigment Yellow 168, C.I. Pigment Yellow 169, C.I. Pigment Yellow 170, C.I. Pigment Yellow 171, C.I. Pigment Yellow 172, C.I. C.I. Pigment Yellow 175, C.I. Pigment Yellow 176, C.I. Pigment Yellow 177, C.I. Pigment Yellow 179, C.I. Pigment Yellow 180, C.I. Pigment Yellow 181, C.I. Pigment Yellow 182, C.I. Pigment Yellow 185, C.I. C.I. Pigment Yellow 193, C.I. Pigment Yellow 194, C.I. Pigment Yellow 199, C.I. Pigment Yellow 213, C.I. Pigment Yellow 214 and other yellow pigments. In the present invention, C.I. Pigment Yellow 138 is particularly preferred.

In some embodiments, as the blue pigment in the coloring agent of the present invention, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64 can be listed , 80 and other blue pigments. Alternatively, in some embodiments, the colorant may include violet pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and the like.

In some embodiments, pigments may be used alone or in a combination of two or more of them to increase color purity.

In some embodiments, in addition to the green pigment, yellow pigment and/or blue pigment, the colorant resin composition may have other colors of pigments, or green, yellow, blue, or other colors according to actual needs. dye.

In addition, in this invention, a pigment and a dye can be used individually or in mixture of 2 or more types, respectively. As another pigment, a yellow pigment, a brown pigment, a purple pigment, etc. can be illustrated.

The dyes that can be used in the examples are not particularly limited, and well-known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of the dyes include compounds classified as substances having a hue other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Notes (Shiyesha). In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, square dyes Acid dyes, acridine dyes, styryl dyes, coumarin dyes, cyanine dyes, anthraquinone dyes, azo dyes, squaraine dyes, dipyrromethene dyes, quinoline dyes, porphyrin dyes, quinoline dyes Fluorine dyes and nitro dyes, etc.

In some embodiments, the colorant in the colored resin composition is preferably 5 to 50 parts by weight, more preferably 10 to 25 parts by weight, if the total weight of the colored resin composition is 100 parts by weight.

According to actual needs, the coloring resin composition may also contain a dispersant, so that the colorant can be uniformly dispersed in the solution. As said dispersing agent, cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, etc. surfactants are mentioned, for example. These dispersants may be used alone or in combination of two or more. The pigment dispersant is represented by a trade name, and examples include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOREN (manufactured by Kyōeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), and EFKA (manufactured by CIBA Corporation) , Adisper (manufactured by Ajinomoto fine-techno Co., Ltd.), Disperbyk (manufactured by BYK Chemicals), and the like.

In some embodiments, the alkali-soluble resin of the colorant resin composition may include a resin monomer unit and a silane-based monomer unit, wherein the resin monomer unit contains an unsaturated double bond and/or an epoxy group.

In some embodiments, the alkali-soluble resin of the colorant resin composition may be a structure whose side chain is alkane or cycloalkane, and the side chain structure may contain acid branch functional groups or unsaturated bonds.

In some embodiments, the alkali-soluble resin of the colorant resin composition may, for example, but not be limited to, have (meth)acrylic acid derived structural units.

In some embodiments, the alkali-soluble resin may have a structural unit derived from a monomer (m2-1) and a monomer (hereinafter referred to as a monomer having a cyclic ether structure having 2 to 4 carbons and an ethylenically unsaturated bond) It is a copolymer of structural units derived from "monomer (m2-2)"). The above-mentioned copolymer may contain other constituent units. As the other structural unit, for example, a structural unit derived from a monomer (hereinafter referred to as "monomer (m2-3)") different from the monomer (m2-1) and the monomer (m2-2), or having an alkene It is a structural unit of unsaturated bonds, etc. In the copolymer, each of the above-mentioned structural units contains only one type, but may contain two or more types.

Examples of the monomer (m2-1) include (1) acrylic acid, methacrylic acid (MAA), succinic acid (SA), crotonic acid, o-, m-, p-vinyl benzoic acid, etc. Saturated monocarboxylic acids; (2) maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4, 5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids Carboxylic acids; (3) methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1] Hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy- Bicyclic unsaturated compounds containing carboxyl groups such as 6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, etc.; (4) Maleate Acid anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2, Unsaturated dicarboxylic acid anhydrides such as 3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; ( 5) Mono-[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acrylooxyethyl] phthalate and other polyvalent carboxylic acids of divalent or higher Unsaturated mono[(meth)acrylooxyalkyl]esters; or (6) unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as (6) α-(hydroxymeth)acrylic acid, and the like.

Among these, acrylic acid (AA), methacrylic acid (MAA), maleic anhydride, etc. are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

The monomer (m2-2) refers to, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (eg, an oxirane ring, an oxetane ring, or a tetrahydrofuran ring) and an ethylenically unsaturated bond.

Examples of the monomer (m2-2) include a monomer (m2-2-1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (m2-2-1)" "), a monomer (m2-2-2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (m2-2-2)"), or A monomer (m2-2-3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (m2-2-3)") and the like.

Examples of the monomer (m2-2-1) include monomers (m2-2-1a) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "" Monomer (m2-2-1a)"), monomer (m2-2-1b) having a structure in which alicyclic unsaturated hydrocarbons are epoxidized (hereinafter sometimes referred to as "monomer (m2-2-1b)" ”).

As the monomer (m2-2-1a), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Examples of the monomer (m2-2-1a) include glycidyl (meth)acrylate (GMA), β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl (meth)acrylate, and glycidyl (meth)acrylate. Glyceryl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, alpha-methyl-o-vinylbenzyl Glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl) Styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene , 2,3,4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl) base) styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.

Examples of the monomer (m2-2-1b) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Co., Ltd.), 3,4-Epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMERA400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMERA400; Co., Ltd.) Company Daicel manufacturing) and so on.

Examples of the monomer (m2-3) include methyl (meth)acrylate (MMA), ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-butyl (meth)acrylate, 3-butyl (meth)acrylate, 2-Ethylhexyl acrylate (2-Ethylhexyl acrylate; 2EHA), 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, ( Lauryl meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, (meth)acrylate ) tricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate (in this technical field, as a common name, referred to as "dicyclopentyl (meth)acrylate". In addition, sometimes referred to as "(meth)acrylate tricyclodecyl"), (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]decen-8-yl ester (in this technical field, as a common name, called "(methyl) (meth)dicyclopentenyl acrylate”), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate , (meth)acrylates such as propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate (BZMA); (meth)acrylic acid (meth)acrylates containing hydroxyl groups such as 2-hydroxyethyl ester (HEMA) and 2-hydroxypropyl (meth)acrylate; diethyl maleate, diethyl fumarate, diethyl itaconic acid Dicarboxylic acid diesters such as esters; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2- alkene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1] Hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2. 1] Hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]heptane -2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5 -Methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1 ]hept-2-ene, 5-3-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-benzene Oxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxy) carbonyl) bis Bicyclic unsaturated compounds such as cyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide (CHMI), N-benzylmaleimide , N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6- Maleimide caproate, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl)maleimide and other dicarbonylimine derivatives ; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, chloride Ethylene, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

Among these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, and N-cyclohexylmaleimide are preferred. Imide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, and benzyl(meth)acrylate, etc.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryloyl group. The first adhesive polymer (B1) having such a structural unit can be obtained by making a polymer containing a structural unit derived from the monomer (m2-1) and a structural unit derived from the monomer (m2-2) , and react with monomers having reactive groups and ethylenically unsaturated bonds with the aforementioned constituent units.

As a constitutional unit having an ethylenically unsaturated bond, for example, a constitutional unit obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid unit, or by adding 2 to a maleic anhydride unit can be used. - A structural unit obtained by hydroxyethyl (meth)acrylate, a structural unit obtained by adding (meth)acrylic acid to a glycidyl (meth)acrylate unit, and in a structural unit having a hydroxyl group A structural unit obtained by adding a carboxylic acid anhydride, etc.

In some embodiments, the alkali-soluble resin comprises a photocurable resin, the photocurable resin has a weight average molecular weight (Mw) of less than 20,000 and a potassium hydroxide (KOH) titration acid value of less than 100 mg KOH/g . The unit of potassium hydroxide (KOH) titration acid value can also be simply expressed as mg/g in the text. In some embodiments, the potassium hydroxide (KOH) titratable acid value of the photocurable resin is less than 55 mg/g. In one embodiment, the photocurable resin contained in the alkali-soluble resin may be a copolymer of the structure represented by the following formula (I) (explained below).

式(I) In some embodiments, the alkali-soluble resin of the colorant resin composition may, for example, comprise a copolymer having a structure represented by the following formula (I):

Formula (I)

Among them, m, e, f, and g are positive integers.

In an example, if the entire molecular chain is set to be 100%, m accounts for 1-10% of the polymer chain, e accounts for 20-70% of the polymer chain, f accounts for 20-70% of the polymer chain, and g accounts for 20-70% of the polymer chain. It is 1~35% higher than the polymer chain.

In some embodiments, the copolymer of the structure represented by the above formula (I) contained in the alkali-soluble resin is dicyclopentyl (meth)acrylate (TCDMA)/methyl (meth)acrylate (MMA)/ A photocurable resin of a copolymer of glycidyl (meth)acrylate (GMA)/(meth)acrylic acid (MAA). Here, compounds described in parentheses mean the presence or absence of the words in parentheses, such as the aforementioned dicyclopentyl (meth)acrylate, including dicyclopentyl acrylate, and dicyclopentyl methacrylate the case of esters.

In some embodiments, the main chain of the copolymer of the structure shown in formula (I) comprises: (meth)dicyclopentyl acrylate (TCDMA), which accounts for 3%/mol of the aforementioned main chain; (methyl) ) methyl acrylate (MMA), which accounts for 70%/mol to 27%/mol of the aforementioned main chain; and glycidyl (meth)acrylate (GMA), which accounts for 27%/mol to 70% of the aforementioned main chain /mol.

According to some embodiments of the present disclosure, the photocurable resin included in the alkali-soluble resin is, for example, the copolymers prepared in Preparation Examples 3-8.

Furthermore, in some embodiments, the photocurable resin included in the alkali-soluble resin, such as but not limited to the structure shown in the above formula (I), has a weight-average molecular weight of less than 20,000, and potassium hydroxide (KOH) The titration acid value is preferably less than 55 mg/g; the weight average molecular weight is less than 10,000, and the titration acid value of potassium hydroxide (KOH) is less than 100 mg/g.

In addition, according to some comparative examples, if the photocurable resin contained in the alkali-soluble resin, such as but not limited to the structure shown in the above formula (I), has a weight-average molecular weight greater than 10,000 and a potassium hydroxide (KOH) titration acid value When it is greater than 55 mg/g, the photoresist structure formed will have a deep undercut depth, and may have local peeling (Peeling) or uneven bright and dark lines.

In some embodiments, the photocurable resin contained in the alkali-soluble resin, such as but not limited to the structure shown in the above formula (I), has a weight average molecular weight of less than 10,000, and the photocurable resin contains- The COOH group accounts for about 3.5%/mol to about 31.2%/mol of the photocurable resin. In some other embodiments, the weight average molecular weight of the photocurable resin is less than 10,000, and the -COOH group contained in the photocurable resin accounts for about 3.5%/mol to about 10%/mol of the photocurable resin. .

In some embodiments, the photocurable resin included in the alkali-soluble resin, such as but not limited to the structure shown in the above formula (I), has a weight average molecular weight between 6,000 and 20,000, and the photocurable resin is The -COOH groups included are less than about 7 %/mol of the photocurable resin.

In some embodiments, the ratio (Binder/Monomer Ratio) of the photocurable resin contained in the alkali-soluble resin to the monomer of the polymerizable unsaturated compound in the colored resin composition is about 6.7% to about 300%. In some other embodiments, the ratio of the aforementioned photocurable resin to the aforementioned monomers of the polymerizable unsaturated compound is about 6.7% to about 166.7%.

Furthermore, according to some embodiments of the present disclosure, the alkali-soluble resin of the colored resin composition may further include a thermosetting resin in addition to the photocurable resin. In some embodiments, the aforementioned thermosetting resin may include a copolymer of EDCPA/methacrylic acid (MAA), wherein the trade name "E-DCPA" (manufactured by Daicel Co., Ltd.) is a 3,4-epoxy tricyclic acrylic acid containing [5.2.1.0 ^2,6 ] Decan-8-yl ester and 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ] Decan-9-yl acrylate in a molar ratio of 50:50 mixture. Furthermore, in some embodiments, the aforementioned thermosetting resin comprises resin I-1 (as shown in chemical formula 1-4) and resin I-2 (as shown in chemical formula 1-5) prepared in the following preparation examples 9-11. , resin J-1 (as shown in chemical formula 1-4), resin J-2 (as shown in chemical formula 1-5), resin K-1 (as shown in chemical formula 1-4), resin K-2 (as shown in chemical formula 1-5), or a combination of the aforementioned resins. Table 3 also lists the composition ratio of resins I, J and K, the molecular weight and the ratio of -COOH groups.

In some embodiments, the weight average molecular weight of the thermosetting resin included in the alkali-soluble resin is between about 5,000 and about 20,000, and the potassium hydroxide (KOH) titration acid value is between about 100 mg/g and about 120 mg/g. In some other embodiments, the alkali-soluble resin comprises a thermosetting resin having a weight average molecular weight of less than about 10,000.

In some embodiments, the thermosetting resin contained in the alkali-soluble resin accounts for about 8.9% to about 10% by weight of the coloring resin composition, and the photocurable resin contained in the alkali-soluble resin accounts for the coloring composition. About 1.5% to about 17.4%. In some other embodiments, the photocurable resin contained in the alkali-soluble resin accounts for about 1.5% to about 14.6% by weight of the coloring composition, and the potassium hydroxide (KOH) titration acid value is less than about 50 mg/g.

Furthermore, in some embodiments, the thermosetting resin contained in the alkali-soluble resin contains -COOH groups accounting for about 18 mol % of the thermosetting resin, or less than about 18 mol %. In one embodiment, the alkali-soluble resin comprises a thermosetting resin and a photosetting resin, wherein the -COOH group contained in the thermosetting resin accounts for about 18 mol % of the thermosetting resin, and the weight average molecular weight of the photosetting resin is less than 10,000.

According to some embodiments, the polymerizable unsaturated compound of the colored resin composition may be a monomer polymerized by reactive radicals and/or acids generated by a photopolymerization initiator, such as, but not limited to, polymerizable ethylene. Sexually unsaturated bonds, such as (meth)acrylate compounds. Here, the compound described using parentheses means including the presence or absence of the characters in the parentheses, such as the aforementioned (meth)acrylate compound, the case of including an acrylate compound, and a methacrylate compound. The polymerizable unsaturated compound may also be referred to as a polymerizable compound.

In some embodiments, the polymerizable unsaturated compound is, for example, a photopolymerizable monomer, which may include, but is not limited to, at least one selected from the group consisting of: Nonylphenyl carboxylate acrylate Polymerization of alcohol ester, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc. with one ethylenically unsaturated bond Compounds; 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethyl di(meth)acrylate Polymerizable compounds having two ethylenically unsaturated bonds, such as glycol esters, bis(acrylooxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate; and three Trimethylolpropane (meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, Tripentaerythritol octa (meth)acrylate, tripentaerythritol hepta (meth)acrylate, tripentaerythritol octa (meth)acrylate, pentaerythritol ten (meth)acrylate, pentaerythritol nona (meth)acrylate, Tris(2-(meth)acryloyloxyethyl)isocyanate, ethylene glycol tetra(meth)acrylate-modified pentaerythritol, ethylene glycol hexa(meth)acrylate-modified dipentaerythritol, tetra(methyl)acrylate ) Propylene glycol modified pentaerythritol acrylate, propylene glycol hexa(meth)acrylate modified dipentaerythritol, tetra(meth)acrylate caprolactone modified pentaerythritol, hexa(meth)acrylate modified dipentaerythritol, etc. A polymerizable compound having three ethylenically unsaturated bonds. In some embodiments, the polymerizable unsaturated compound is, for example, a compound having an ethylenically unsaturated double bond. In some embodiments, the polymerizable unsaturated compound is, for example, a polymerizable compound having three ethylenically unsaturated double bonds.

Commercially available products of the polymerizable unsaturated compound include KAYARAD (registered trademark) DPHA (Nihon Kayaku Co., Ltd.) and trade name "A-TMM-3LM-N" (pentaerythritol triacrylate; Shin-Nakamura Chemical Industry Co., Ltd. ).

In some embodiments, the weight average molecular weight of the polymerizable unsaturated compound is, for example, 150 or more and 2,900 or less. In some embodiments, the weight average molecular weight of the polymerizable unsaturated compound is, for example, 250 or more and 1,500 or less.

In some embodiments, the polymerizable unsaturated compound may account for about 1-10 wt % of the colored resin composition.

According to some embodiments, the photopolymerization initiator can be any compound that can generate active radicals, acids, etc. under the action of light, thereby starting the photopolymerization reaction, and is not particularly limited.

In some embodiments, the photopolymerization initiator of the colored resin composition may include, but is not limited to, at least one selected from the group consisting of: O-acyloxime (O-acyloxime) Compounds, alkyl phenyl ketone compounds, bisimidazole compounds, triazine compounds, acyl phosphine oxide, benzoin compounds, benzophenone compounds, quinone compounds, 10-butyl-2-chloroacridine pyridone, benzyl, methyl phenylformate, acetophenone, and titanium cyclopentadienyl compounds.

In some embodiments, the photopolymerization initiator preferably includes at least one selected from the group consisting of: O-acyl oxime compounds, alkyl phenyl ketone compounds, bisimidazole compounds, Acetophenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds. For example, in the case of using an O-acyl oxime compound as the photopolymerization initiator (D), Irgacure® OXE-01 (BASF Corporation), Irgacure® OXE-02 (BASF Corporation), N-1919 ( ADEKA Corporation) and other commercially available products.

The above-mentioned O-acyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bonding end.

Examples of the above-mentioned O-acyl oxime compound include N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, Oxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)- 3-Cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazole-3 -yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Oxolatylmethoxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-( 2-Methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6- (2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as IRGACURE OXE01 and OXE02 (the above are manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) can be used. Among them, the O-acyl oxime compound is preferably selected from N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, yl-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine and N-benzyloxy-1-(4-phenylsulfanylphenyl)-3 -At least one of cyclopentylpropan-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylsulfanylphenyl)octan-1-one- 2-Imine. In the case of these O-acyl oxime compounds, a high-brightness color filter tends to be obtained.

The above-mentioned alkyl phenyl ketone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

As a compound having a partial structure represented by formula (d2), for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-di Methylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl base]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercially available products such as IRGACURE 369, 907, and 379 (the above are manufactured by BASF Corporation) can be used.

As a compound having a partial structure represented by formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4- (2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1- Oligomers of ketones, α,α-diethoxyacetophenone, benzalkonium dimethyl ketal, etc.

In terms of sensitivity, as the alkyl phenyl ketone compound, a compound having a partial structure represented by the formula (d2) is preferable.

Examples of the above-mentioned triazine compound include 2,4-bis-trichloromethyl-6--4-methoxyphenyl-1,3,5-triazine, 2,4-bis-trichloromethyl-6 -4-Methoxynaphthyl-1,3,5-triazine, 2,4-bistrichloromethyl-6-pipronyl-1,3,5-triazine, 2,4-bistrichloromethane yl-6-4-methoxystyryl-1,3,5-triazine, 2,4-bistrichloromethyl-6-[2-(5-methylfuran-2-yl)vinyl ]-1,3,5-triazine, 2,4-bistrichloromethyl-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4- Bistrichloromethyl-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bistrichloromethyl- 6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

As said acyl phosphine oxide compound, 2, 4, 6- trimethylbenzyl diphenyl phosphine oxide etc. are mentioned. Commercially available products such as IRGACURE (registered trademark) 819 (manufactured by BASF) can be used.

As said biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis (Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62- 174204 Gazette, etc.), imidazole compounds in which the phenyl group at the 4,4', 5,5'-position is substituted with an alkoxycarbonyl group (for example, see Japanese Patent Laid-Open No. 7-10913, etc.), and the like.

Other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Esters, 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(3-butylperoxycarbonyl) Benzophenone compounds such as benzophenone and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthraquinone, 2-ethylanthraquinone and camphorquinone; 10-butyl- 2-Chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc. Preferably, these polymerization initiators may be used in combination with a polymerization initiator (especially amines) described later.

The acid generators include 4-hydroxyphenyldimethyl perylene-p-toluenesulfonate, 4-hydroxyphenyldimethyl perylene hexafluoroantimonate, and 4-acetoxyphenyldimethylene Acetyl-p-toluenesulfonate, 4-Acetyloxyphenylmethylbenzyl-hexafluoroantimonate, triphenyl-p-toluenesulfonate, triphenyl-perylene hexafluoroantimonate , Diphenyliodonium-p-toluenesulfonate, onium salts such as diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin tosylate, etc.

In some embodiments, the photopolymerization initiator may account for about 0.1 wt % to 10 wt % of the colored resin composition.

In some embodiments, the solvent of the colored resin composition may include, but is not limited to, at least one selected from the group consisting of: an ester solvent (herein meaning a molecule containing -COO- Solvents that do not contain -O-), ether solvents (referred to herein as solvents that contain -O- but not -COO- in the molecule), ether ester solvents (referred to herein as those that contain -COO- and -O- solvent), ketone solvent (here means a solvent containing -CO- but not -COO- in the molecule), alcohol solvent (here means containing OH but not -O- in the molecule, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclic Hexanol acetate and γ-butyrolactone, etc.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3- Methoxy-3-methylbutanol, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol diethylene glycol Butyl ether, anisole, phenethyl ether and methyl anisole, etc.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone (cyclohexanone, CHN) and isophorone, etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

As the aromatic hydrocarbon solvent, benzene, toluene, xylene, 1,3,5-trimethylbenzene and the like can be mentioned.

As an amide solvent, N,N- dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. are mentioned.

Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120° C. or higher and 180° C. or lower is preferable from the viewpoint of coatability and drying properties. As the solvent, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, and diethylene glycol monomethyl ether are preferable ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether Acetate, propylene glycol monomethyl ether, N-methylpyrrolidone, ethyl lactate and ethyl 3-ethoxypropionate.

In some embodiments, the content of the solvent may be about 30 wt % to about 95 wt %, or 40 wt % to 60 wt %, eg, about 45 wt %, relative to the total amount of the colored resin composition. When the content of the solvent is appropriate, the flatness at the time of coating can be improved, and the color density is not insufficient when the color filter is formed, so that the display characteristics can be further improved.

In order to make the above-mentioned and other objects, features, and advantages of the present disclosure more obvious and easy to understand, the preparation of colored resin compositions in several experimental examples and comparative examples is given below, and the colored resin compositions in these examples are coated After being placed on the substrate, several inspections, analyses and evaluations were carried out to observe the characteristics of the film layer containing the composition. These experimental contents can specifically illustrate the effect achieved by the coloring resin composition according to the embodiments of the present disclosure, and the characteristics of the color photoresist composition prepared by applying the present disclosure. However, the following examples and comparative examples are only used for illustration, and should not be construed as a limitation of the implementation of the present disclosure.

In addition, the coloring resin composition proposed in the experimental example, the formation of the coating film and the evaluation method of the film layer characteristics are briefly described below. In the subsequent analysis of the detection results of each experimental example, the detection and evaluation methods will not be repeated.

[Formation of coating film]

(a) First, on a substrate with a thickness of about 0.4 mm to about 0.7 mm, the coloring resin composition of each experimental example is applied by spin coating;

(b) placing the substrate coated with the colored resin composition on a hot plate at about 80° C. to about 90° C., and pre-baking for about 38 seconds to about 88 seconds to remove the composition most solvents; and

(c) After the substrate is cooled, and after the exposure step is performed using an exposure machine, the substrate is moved to a developing machine to perform the developing step, so as to form a coloring film layer on the substrate.

[Development process conditions]

Development process: The development pressure is 0.07 megapascal (MPa) and the development time is 50 seconds for development using an alkaline developer. After that, rinse with clean water (deionized water??), the rinse pressure is 0.1 MPa (MPa), and the rinse time is 40 seconds.

After the development is completed, a colored film layer is formed on the substrate.

[Evaluation method of colored film layer]

In the present disclosure, the colored resin composition of each experimental example was photographed on the edge of the colored film layer formed on the substrate with a scanning electron microscope (SEM) (model: HITACH Regulus 8100) after the steps of pre-baking, exposure and development. and the undercut part to observe the cross-sectional shape of the film and measure the undercut depth. For the definition of the undercut depth, please refer to the above-mentioned depth d of the photoresist structure 21 along the X direction as shown in FIG. 2A and related descriptions.

Furthermore, an optical microscope (model: NiKon eclipse LV150N) was also used to take OM photos of the upper part of the colored film layer formed on the substrate at a magnification of 20 times and 50 times, respectively, to inspect and observe the coloring film layer formed on the substrate. Whether the edge is complete; for example, when viewed from the top of the coloring film layer, if the formed coloring film layer includes several strip-shaped photoresist structures (as shown in Figure 2B), then inspect these strip-shaped photoresist structures the edges of the photoresist for peeling, sag or other defects, and assess whether these defects account for a disproportionately high percentage of all photoresist structures.

(a) The evaluation criteria for the undercut depth of the colored film layer formed on the substrate are as follows:

The undercut depth of less than or equal to 1 μm (≦ 1 μm) is evaluated as O, indicating that the colored film layer has good undercut characteristics;

An undercut depth in the range of more than 1 μm to less than 3 μm (ie, 1 μm < undercut depth μm < 3 μm) is evaluated as Δ, indicating that the pigmented film layer has acceptable undercut characteristics; and

An undercut depth of 3 μm or more (≧ 3 μm) was evaluated as X, indicating that the undercut characteristics of the colored film layer were poor.

(b) Check the colored film layer formed on the substrate with an optical microscope, and the evaluation criteria for the edge integrity of the film layer are as follows:

If the edge of the colored film layer formed on the substrate is inspected with an optical microscope, the line color is uniform, and there is no concave defect at all, it is evaluated as 0, indicating that the colored film layer has excellent edge integrity;

If the color of the edge of the colored film layer is slightly uneven, it is evaluated as Δ, indicating that the colored film layer has acceptable edge integrity. In the experiment, the proportion of all edge defects in all film structures is low Below 30%, it is rated as "minor";

If the edge of the colored film layer is inspected and the color of the lines is mostly uneven or collapsed, the evaluation is X, indicating that the colored film layer has an unacceptable edge integrity.

Comprehensive evaluation of the undercut results and OM photos is carried out, and the judgment criteria are as follows: undercut result OM Overall rating O O ◎ O Δ O Δ O O Δ Δ Δ X X X

<Related experiment 1: Different photocurable resins are included in the alkali-soluble resin of the colored resin composition>

Please refer to Table 1 and Table 2. In the related experiment 1, the compositions (including components and their weight percentages) of the colored resin compositions of each experimental example and the comparative example are listed in Table 1. Table 2 lists the types and characteristics of the photocurable resins used in each of the experimental examples and comparative examples (such as their weight-average molecular weight and the -COOH group contained), and the composition formed by the composition comprising the photocurable resin. The undercut depth of the pigmented film layer.

The alkali-soluble resins in each experimental example listed in Table 1 include thermosetting resin-I (as in the subsequent preparation example 9) and photocurable resins (including 7 kinds and/or different proportions of self-provided resins, as in the subsequent preparations Example 1-Preparation Example 7). For the convenience of displaying the table briefly, the components/copolymers in Table 1 are represented by commercially available trade names and/or component abbreviations, and the monomer names and proportions of each component/copolymer are listed at the bottom of Table 1 and in Table 2. .

Table 1 type Product name Experiment 1-1 Experiment 1-2 Experiments 1-3 Experiments 1-4 Colorant B15:6 20.9% Thermosetting resin I 8.9% photocurable resin A 10.0% B 10.0% C 10.0% D 10.0% Monomers of polymerizable unsaturated compounds DPHA 10.0% photopolymerization initiator OXE-01 5% solvent PGMEA 45% (Continued from Table 1) type Product name Experiments 1-5 Experiments 1-6 Experiments 1-7 Colorant B15:6 20.9% Thermosetting resin I 8.9% E 10.0% F 10.0% G 10.0% Monomers of polymerizable unsaturated compounds DPHA 10.0% photopolymerization initiator OXE-01 5% solvent PGMEA 45% Colorant Pigment Blue B15:6: Organic blue pigment ( purchased from Nippon Pigment ) Thermosetting resin material-I: Please refer to Preparation Example 9 Polymerizable unsaturated compound monomer DPHA: Dipentaerythritol hexaacrylate (KAYARAD ( Registered trademark)) Photopolymerization initiator OXE-01: O-acyloxime compound ( purchased from BASF ) Solvent PGMEA: propylene glycol monomethyl ether acetate ( purchased from Yuwa Trading )

Table 2 experiment Name of photocurable resin Monomer ratio of copolymer (%/mol) Molecular weight (Mw) Undercut depth COOH group 1-1 A TCDMA/ BZMA/ MAA/ (GMA+MMA) = 10/ 50/ 25/ 15 27000 3.55 μm 25%/mol 1-2 B BZMA/MAA = 60/40 10500 9.02 μm 40%/mol 1-3 C TCDMA/MMA/MAA/(MAA+GMA) = 3/27/6.9/63.1 17200 1.41 μm 6.9%mol 1-4 D TCDMA/ MMA/ MAA / (MAA+GMA) = 3/ 27/ 31.2/ 38.8 6100 1.01 μm 31.2%mol 1-5 E TCDMA/ MMA/ MAA/ (MAA+GMA) = 3/ 27/ 9.1/ 60.9 6400 0.36μm 9.1%mol 1-6 F TCDMA/ MMA/ MAA/ (MAA+GMA) = 3/70/ 3.5/ 23.5 6500 0.251μm 3.5%mol 1-7 G TCDMA/ MMA/ MAA/ (MAA+GMA) = 3/ 27/ 31.2/ 38.8 23900 7.87 μm 31.2%mol TCDMA: Dicyclopentyl (meth)acrylate BZMA: Benzyl (meth)acrylate MAA: Methacrylate MMA: Methyl (meth)acrylate GMA: Glycidyl (meth)acrylate

TCDMA (m)=10mol %, BZMA (n)=50 mol %, MAA (p)=25 mol % , MAA+GMA (f)=15 mol %   1-2 [化學式1-2]

BZMA(n) = 60 % / mol, MAA(p) = 40 % / mol 1-3~ 1-7 [化學式1-3]

以實驗1-3為例，化學式1-3中: TCDMA(m) =3% / mol, MMA(e) =27% / mol, GMA+MAA (f) = 63.1% / mol, MAA(p) = 6.9% / mol (實驗1-4~1-7的單體成分比例係參照表2) Furthermore, the photocurable resins corresponding to experiments 1-1 to 1-7 listed in Table 2, their chemical formulas and monomer ratios (mol %) are organized as follows: experiment chemical formula Monomer ratio (mol %) 1-1 [Chemical formula 1-1]

TCDMA (m)=10mol %, BZMA (n)=50 mol %, MAA (p)=25 mol %, MAA+GMA (f)=15 mol % 1-2 [Chemical formula 1-2]

BZMA(n) = 60 % / mol, MAA(p) = 40 % / mol 1-3~ 1-7 [Chemical formula 1-3]

Taking experiment 1-3 as an example, in chemical formula 1-3: TCDMA(m) =3% / mol, MMA(e) =27% / mol, GMA+MAA (f) = 63.1% / mol, MAA(p) = 6.9% / mol (refer to Table 2 for the proportion of monomer components in experiments 1-4~1-7)

In related experiment 1, the characteristics of the colored resin composition of each experimental example, the edge and undercut portion of the film layer were inspected by scanning electron microscope (SEM) after the colored film layer formed on the substrate, and the measured undercut depth The evaluation results of (undercut depth) are listed in Table 3. Table 3 and Figures 3A to 3G can be referred to at the same time, wherein Figures 3A to 3G are respectively simple schematic diagrams of the film edge and the undercut portion of the SEM images according to experiments 1-1 to 1-7, and the figures show The partial photoresist structure 31 and the undercut depth d on the substrate 30 of each experimental example. In addition, the evaluation results of whether the edges of the colored film layers of each experimental example were observed with an optical microscope with a magnification of 20 times and 50 times, respectively, are also listed in Table 3.

table 3 Experimental example photocurable resin molecular weight Acid value Undercut depth Undercut Evaluation (SEM) Colored Film Edge Integrity (OM 20X & 50X) Overall rating 1-1 A 27000 86.9 3.55 μm X X X 1-2 B 10500 120 9.02 μm X X X 1-3 C 17200 28 1.41 μm △ O O 1-4 D 6100 97 1.01 μm △ △ △ 1-5 E 6400 35.4 0.36 μm O O ◎ 1-6 F 6500 33.7 0.25 μm O O ◎ 1-7 G 23900 96 7.87 μm X X X

According to the results of the above-mentioned related experiment 1, the alkali-soluble resins of the coloring resin compositions proposed in Experimental Examples 1-3, 1-4, 1-5 and 1-6 used, for example, a bicyclic (meth)acrylic acid. Photocurable resin of copolymer of amyl ester (TCDMA)/methyl (meth)acrylate (MMA)/glycidyl (meth)acrylate (GMA)/(meth)acrylic acid (MAA), in appropriate molecular weight And in the case of matching acid value, such as its molecular weight is less than 20000, and potassium hydroxide (KOH) titration acid value is less than 100 mg/g, after the coloring film layer is formed on the substrate, it can improve the undercut depth of the film layer and form a complete edge. For example, the photocurable resins used in Experimental Examples 1-3 to 1-6 have molecular weights of 17200, 6100, 6400, and 6500 (all lower than 20000) and acid values of 28, 97, 35.4, and 33.7 mg/g, respectively. (all less than 100 mg/g), the formed coloring film layer has a good mushroom-shaped cross section (as shown in Figures 3C~3F), and the undercut depth is less than 1.5μm, and the coloring formed on the substrate is inspected with an optical microscope. The edges of the film layers also have good or acceptable edge integrity.

Furthermore, in some embodiments, the compounds used include, for example, dicyclopentyl (meth)acrylate (TCDMA)/methyl methacrylate (MMA)/glycidyl (meth)acrylate (GMA)/(methyl methacrylate) ) Photocurable resin of copolymer of acrylic acid (MAA), the molecular weight is less than 20000, and the acid value of potassium hydroxide (KOH) titration is less than 55 mg/g, such as experimental examples 1-3, 1-5 and 1-6 The acid value is less than 40mg/g, and the edge of the coloring film layer formed on the substrate is inspected with an optical microscope, the line color is uniform, and the edge of the coloring film layer formed on the substrate has good edge integrity. However, the photocurable resin of Experimental Example 1-4 has an acid value of 97 mg/g. After exposure and development on the substrate to form a colored film layer, the color of the edge of the colored film layer is slightly uneven, but the color is still acceptable. Within the standard of completeness (that is, the inspection machine will not produce an excessive number of false positives).

Furthermore, in some embodiments, the compounds used include, for example, dicyclopentyl (meth)acrylate (TCDMA)/methyl methacrylate (MMA)/glycidyl (meth)acrylate (GMA)/(methyl methacrylate) ) The photocurable resin of the copolymer of acrylic acid (MAA), the molecular weight is less than 10000, and the potassium hydroxide (KOH) titration acid value is less than 55 mg/g, such as experimental examples 1-5 and 1-6, the coloring formed The undercut depth of the film layer can be reduced by less than 0.4 μm, and the edge of the colored film layer formed on the substrate is inspected with an optical microscope, and the edge integrity is also very excellent.

<Related Experiment 2: A photocurable resin containing the same components but different component ratios in the alkali-soluble resin of the colored resin composition>

Please refer to Table 4 and Table 5. In the relevant experiment 2, the components of the thermosetting resin, the photosetting resin and the monomer of the polymerizable unsaturated compound of the colored resin composition of the experimental examples 2-1~2-7, and the ratio (%) ) (Binder/Monomer Ratio) series in Table 4. In the experimental examples 2-1 to 2-7, the product name I was selected as a thermosetting resin, the product name F was selected as a photocurable resin, and DPHA was selected as a monomer of a polymerizable unsaturated compound.

Table 4 type Product name Experiment 2-1 Experiment 2-2 Experiment 2-3 Experiment 2-4 Experiment 2-5 Experiment 2-6 Experiment 2-7 Thermosetting resin I 20 photocurable resin F 5 10 20 30 40 50 60 Monomers of polymerizable unsaturated compounds DPHA 75 70 60 50 40 30 20 For the composition of the thermosetting resin I, please refer to Table 6. The composition of the photocurable resin F is as described above.

In the relevant experiment 2, the characteristics of the colored resin composition of each experimental example, the edge and undercut portion of the film layer were inspected by scanning electron microscope (SEM) after the colored film layer formed on the substrate, and the measured undercut depth The evaluation results of (undercut depth) are listed in Table 5. Table 5 and Figures 4A to 4F can be referred to at the same time, wherein Figures 4A to 4G are respectively a simple schematic diagram of the film edge and the undercut portion of the SEM images according to Experimental Examples 2-1 to 2-7, and the figures show The partial photoresist structure 41 and the undercut depth d on the substrate 40 of each experimental example are shown. Furthermore, the evaluation results of whether the edges of the colored film layers in each experiment were observed with an optical microscope with a magnification of 20 times and 50 times, respectively, are also listed in Table 5.

table 5 Experimental example Photocurable resin/polymerizable unsaturated compound monomer Undercut depth Undercut Evaluation (SEM) Colored Film Edge Integrity (OM 20X & 50X) Overall rating Experiment 2-1 6.7% 0.271 μm ○ ○ ◎ Experiment 2-2 14.3% 0.204 μm ○ ○ ◎ Experiment 2-3 33.3% 0.582 μm ○ ○ ◎ Experiment 2-4 60% 0.591 μm ○ ○ ◎ Experiment 2-5 100% 0.715 μm ○ ○ ◎ Experiment 2-6 166.7% 0 μm ○ ○ ◎ Experiment 2-7 300% 0μm ○ △ ○

According to the results of the above-mentioned related experiment 2, the alkali-soluble resin of the coloring resin composition proposed in Experimental Examples 2-1 to 2-7 uses the same thermosetting resin I and photosetting resin F, wherein the thermosetting resin I is (please refer to the preparation method of table 6 and preparation example 9 for composition ), photocurable resin F series is TCDMA/MMA/(GMA+MAA)/MAA=3/70/23.5/3.5 (weight ratio is 3:70:23.5 : 3.5) photocurable resin of the copolymer. In the related experiment 2, the ratio (Binder/Monomer Ratio) of the photocurable resin to the monomer of the polymerizable unsaturated compound of the colored resin composition was further changed. According to the experimental results, when the ratio (Binder / Monomer Ratio) of the photocurable resin to the monomer of the polymerizable unsaturated compound is about 6.7% to about 300%, the formed colored film layer has a good or acceptable mushroom shape Sections (as shown in Figures 4A to 4G), and the undercut depths are all less than 1.0 μm, and the edge of the colored film layer formed on the substrate also has good or acceptable edge integrity when inspected with an optical microscope.

Furthermore, in some embodiments, for example, the ratio (Binder/Monomer Ratio) of the photocurable resin used in Experimental Examples 2-1 to 2-6 relative to the monomer of the polymerizable unsaturated compound is about 6.7% to about 6.7%. At 166.7%, the formed colored film has a good mushroom-shaped section, the undercut depth is less than 1.0 μm, and the edge of the formed colored film on the substrate also has good or even excellent edge integrity when inspected with an optical microscope.

<Related experiment 3: Different thermosetting resins are included in the alkali-soluble resin of the colored resin composition>

Please refer to Table 6 and Table 7. In the relevant experiment 3, the components (such as the monomer ratio) and characteristics (such as the weight average molecular weight and the -OH group contained in the thermosetting resin used in each of the colored resin compositions in the experimental examples 3-1 to 3-3) group and -COOH group), series in Table 6.

Table 6 Thermosetting resin product name Monomer ratio (%mol) molecular weight COOH group I EDCPA/MAA=84.9/15.1 7960 15.1 %/mol J EDCPA/MAA =82.9/17.1 18650 17%/mol K EDCPA/MAA =81.7/18.3 24800 18.3%/mol

[化學式1-4] Furthermore, corresponding to the thermosetting resins listed in Table 6, taking the thermosetting resin K as an example, its chemical formulas 1-4 are as follows:

[Chemical formula 1-4]

In the relevant experiment 3, the characteristics of the colored resin composition of each experimental example, the edge and undercut portion of the film layer were inspected by scanning electron microscope (SEM) after the colored film layer formed on the substrate, and the measured undercut depth The evaluation results of (undercut depth) are listed in Table 7. Table 6 and Figures 5A to 5C can be referred to at the same time, wherein Figures 5A to 5C are respectively simple schematic diagrams of the film edge and the undercut portion of the SEM images according to Experimental Examples 3-1 to 3-3, which are shown in the figures. The partial photoresist structure 51 and the undercut depth d on the substrate 50 of each experimental example are shown. Furthermore, the evaluation results of whether the edges of the colored film layers in each experiment were observed with an optical microscope with a magnification of 20 times and 50 times, respectively, are also listed in Table 7.

Table 7 Experimental example Thermosetting resin molecular weight Acid value Undercut depth Undercut Evaluation (SEM) Colored Film Edge Integrity (OM 20X & 50X) Overall rating Experiment 3-1 I 7960 111 0.715 μm ○ ○ ◎ Experiment 3-2 J 18650 119 0.515 μm ○ △ ○ Experiment 3-3 K 24800 132 6.07 μm X X X

According to the results of the above-mentioned related experiment 3 (using the same photosetting resin but using different thermosetting resins), it is shown that, for example, the alkali-soluble resins of the coloring resin compositions proposed in Experimental Examples 3-1 and 3-2 contain thermosetting The weight average molecular weight of the resin is between about 5000 and about 20000, and the potassium hydroxide (KOH) titration acid value is between about 100 mg/g and about 120 mg/g, and the formed pigmented film layer has good or acceptable mushroom (as shown in Figures 5A and 5B), the undercut depths are all less than 1.0 μm (0.715 μm and 0.515 μm, respectively), and the edge of the colored film layer formed on the substrate is also good or acceptable when inspected with an optical microscope edge integrity.

Furthermore, in some embodiments, the thermosetting resin contained in the alkali-soluble resin, the -COOH group contained therein accounts for about 18 mol % or less than about 18 mol % of the thermosetting resin, such as experimental examples 3-1 and 3-2. The -COOH groups contained in the thermosetting resin account for 15.1 mol% and 17 mol% of the thermosetting resin, respectively, and the formed colored film layer has an undercut depth of less than 1.0 μm and good edge integrity.

In some other embodiments, such as Experimental Example 3-1, the weight average molecular weight of the thermosetting resin contained in the alkali-soluble resin is less than about 10,000, and the acid value of the titration with potassium hydroxide (KOH) is between about 100 mg/g ~ About 120 mg/g. The formed coloring film layer has a good cross section, except that the undercut depth is less than 1.0 μm, and the edge of the coloring film layer formed on the substrate is inspected with an optical microscope, and also has very good edge integrity.

<Related experiment 4: The alkali-soluble resin of the colored resin composition contains two kinds of photocurable resins>

Please refer to Table 8 and Table 9. In the relevant experiment 4, the components and weight percentages of the colored resin compositions of the experimental examples 4-1 to 4-3 are listed in Table 8. In the experimental examples 4-1 to 4-3 listed in Table 8, the alkali-soluble resin system of the colored resin composition of each experimental example comprises a thermosetting resin (for example: 1) and two photosetting resins (for example, 5 % F and another 5% photocurable resin A, C, or H).

In the relevant experiment 4, the components and properties of the thermosetting resin I, photocurable resins A and C used are as described above, and the copolymer monomer ratio (%/mol) of the photocurable resin H is: TCDMA/MMA /MAA/(MAA+GMA) = 3/ 27/ 18.9/ 51.1. The molecular weight of the photocurable resin H was 17800, the undercut depth was 6.11 μm, and the COOH group was 18.9% mol. For the preparation method of the photocurable resin H, refer to the subsequent preparation example 8, for example.

Table 8 type Product name Experiment 4-1 Experiment 4-2 Experiment 4-3 Colorant B15:6 20% Thermosetting resin I 10% photocurable resin F 5% photocurable resin A 5% - - C - 5% - H - - 5% Monomers of polymerizable unsaturated compounds DPHE 10% photopolymerization initiator OXIME 5% solvent PGMEA 45%

In the relevant experiment 4, the characteristics of the colored resin composition of each experimental example, the edge and undercut portion of the film layer were inspected by scanning electron microscope (SEM) after the colored film layer formed on the substrate, and the measured undercut depth The evaluation results of (undercut depth) are listed in Table 9. Table 9 and Figures 6A to 6C may be referred to at the same time, wherein Figures 6A to 6C are respectively simple schematic diagrams of the film edge and the undercut portion of the SEM images according to Experimental Examples 4-1 to 4-3, which are shown in the figures. The partial photoresist structure 61 and the undercut depth d on the substrate 60 of each experimental example are shown. Furthermore, whether the edges of each colored film layer of Experimental Examples 4-1 to 4-3 are complete was observed with an optical microscope with a magnification of 20 times and 50 times, respectively. The evaluation results are also listed in Table 9.

Table 9 Experimental example photocurable resin molecular weight Acid value Undercut depth Undercut Evaluation (SEM) Colored Film Edge Integrity (OM 20X & 50X) Overall rating Experiment 4-1 A 27000 86.9 5.27 μm X X X Experiment 4-3 C 17200 28 0.99 μm ○ ○ ◎ Experiment 4-4 H 17800 66 1.12 μm △ △ △

According to the results of the above-mentioned related experiment 4, two kinds of photocurable resins can be mixed, and a colored film layer with a good cross-sectional shape, an undercut depth close to or less than 1.0 μm, and a complete film edge can also be obtained.

Taking experiment 4-3 as an example, in addition to using the photocurable resin F as in the above-mentioned experimental example 1-6, photocurable resin H is also used, and the weight average molecular weight is less than 20,000, and the formed coloring film layer has a good mushroom. 6C), the undercut depth was 1.12 μm (close to 1.0 μm), and the edges of the pigmented film layer formed on the substrate had acceptable edge integrity under optical microscope inspection.

Furthermore, taking Experiment 4-2 as an example, it uses the photocurable resin F of the above-mentioned experimental example 1-6 and the photocurable resin C of the experimental example 1-3, and the weight average molecular weight is less than 20000. The colored film layer has a good mushroom-shaped cross-section (as shown in Figure 6B), the undercut depth is 0.99 μm (less than 1.0 μm), and the edges of the colored film layer formed on the substrate are inspected with an optical microscope and have good edge integrity.

<Synthesis of photosetting resin and thermosetting resin>

The synthesis methods of the above-mentioned photocurable resins A to H are described in the following Preparation Examples 1 to 8, respectively. The synthetic methods of the above-mentioned thermosetting resins I, J, and K are respectively described in the following Preparation Examples 9 to 11. For the convenience of comparison, the compositions and preparation methods of the photocurable resins A~H used in the above experiments are arranged as follows. experiment photocurable resin Monomer ratio of copolymer (%/mol) Preparation method Molecular weight (Mw) 1-1 A TCDMA/BZMA/MAA/(GMA+MAA) =10/50/25/15 Preparation Example 1 27000 1-2 B BZMA/MAA = 60/40 Preparation Example 2 10500 1-3 C TCDMA/MMA/MAA/(MAA+GMA) = 3/27/6.9/63.1 Preparation Example 3 17200 1-4 D TCDMA/ MMA/ MAA / (MAA+GMA) = 3/ 27/ 31.2/ 38.8 Preparation Example 4 6100 1-5 E TCDMA/ MMA/ MAA/ (MAA+GMA) = 3/ 27/ 9.1/ 60.9 Preparation Example 5 6400 1-6 F TCDMA/ MMA/ MAA/ (MAA+GMA) = 3/70/ 3.5/ 23.5 Preparation Example 6 6500 1-7 G TCDMA/ MMA/ MAA/ (MAA+GMA) = 3/ 27/ 31.2/ 38.8 Preparation Example 7 23900 - H TCDMA/MMA/MAA/(MAA+GMA) = 3/ 27/ 18.9/ 51.1 Preparation Example 8 17800

[Preparation Example 1]:

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet pipe, 213.6 g of propylene glycol monomethyl ether acetate was placed, and the temperature was raised to 90° C. with stirring while replacing with nitrogen. Next, a mixture of 88.2 g (0.50 mol) of benzyl methacrylate, 22.0 g (0.1 mol) of methacrylic acid, tricyclodecyl ester and 28.9 g (0.40 mol) of methyl 4.0 g of t-butylperoxy-2-ethylhexanoate was added to the monomer mixture made of acrylic acid, and dropped into the aforementioned flask from a dropping funnel. After the dropping was completed, the copolymer was produced by stirring at 95° C. for about 3 hours to carry out a copolymerization reaction. Next, after replacing the inside of the flask with air, 21.4 g (0.15 moles) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of hydroquinone (polymerization inhibitor) were added ), carry out ring-opening addition reaction at 120 ℃ for about 6 hours, manufacture copolymer. Next, 221.3 g of propylene glycol monomethyl ether was added to this reaction solution to obtain a copolymer solution (weight average molecular weight 27,000) having a solid content concentration of 30% by mass. The copolymer (photocurable resin A) prepared in Preparation Example 1 has a structural unit as shown in Chemical Formula 1-1.

[Chemical formula 1-1]

[Preparation Example 2]:

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet pipe, 213.6 g of propylene glycol monomethyl ether acetate was placed, and the temperature was raised to 90° C. with stirring while replacing with nitrogen. Next, 4.0 g of t-butylperoxy-2 was added to the monomer mixture consisting of 88.2 g (0.60 mol) of benzyl methacrylate, 22.0 g (0.4 mol) of methacrylic acid, -Ethyl caproate is dropped into the aforementioned flask from a dropping funnel. After the dropping was completed, the copolymer was stirred at 95° C. for 1.5 hours to carry out a copolymerization reaction to produce a copolymer. Next, after replacing the inside of the flask with air, 221.3 g of propylene glycol monomethyl ether was added to obtain a copolymer solution (weight average molecular weight: 10,500) having a solid content concentration of 30% by mass. The copolymer (photocurable resin B) prepared in Preparation Example 2 has a structural unit as shown in Chemical Formula 1-2.

[Chemical formula 1-2]

[Preparation Example 3]:

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet pipe, 213.6 g of propylene glycol monomethyl ether acetate was placed, and the temperature was raised to 90° C. with stirring while replacing with nitrogen. Next, 30.0 g (0.30 moles) of methyl methacrylate, 11.0 g (0.05 moles) of tricyclodecyl methacrylate and 46.9 g (0.65 moles) of methacrylic acid were mixed with To the obtained monomer mixture, 4.0 g of t-butylperoxy-2-ethylhexanoate was added, and it was dropped into the aforementioned flask from a dropping funnel. After the dropping was completed, the copolymer was produced by stirring at 95° C. for about 2 hours to carry out a copolymerization reaction. Next, after replacing the inside of the flask with air, 82.5 g (0.58 moles) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of hydroquinone (polymerization inhibitor) were added ), at 120 DEG C, carry out ring-opening addition reaction for about 7 hours, manufacture copolymer. Next, 221.3 g of propylene glycol monomethyl ether was added to this reaction solution to obtain a copolymer solution (weight average molecular weight 17,200) having a solid content concentration of 30% by mass. The copolymer (photocurable resin C) prepared in Preparation Example 3 has the constituent unit shown in Chemical Formula 1-3.

[Chemical formula 1-3]

[Preparation Example 4]:

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet pipe, 213.6 g of propylene glycol monomethyl ether acetate was placed, and the temperature was raised to 90° C. with stirring while replacing with nitrogen. Next, 30.0 g (0.30 moles) of methyl methacrylate, 11.0 g (0.05 moles) of tricyclodecyl methacrylate and 46.9 g (0.65 moles) of methacrylic acid were mixed with To the obtained monomer mixture, 4.0 g of t-butylperoxy-2-ethylhexanoate was added, and it was dropped into the aforementioned flask from a dropping funnel. After completion of dropping, the copolymer was produced by stirring at 95° C. for about 1 hour to carry out a copolymerization reaction. Next, after replacing the inside of the flask with air, 49.8 g (0.35 moles) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of hydroquinone (polymerization inhibitor) were added ), at 120 ℃, carry out the ring-opening addition reaction for about 3 hours, manufacture copolymer. Next, 221.3 g of propylene glycol monomethyl ether was added to this reaction solution to obtain a copolymer solution (weight average molecular weight 6,100) having a solid content concentration of 30% by mass. The copolymer (photocurable resin D) prepared in Preparation Example 4 has the constituent units shown in the above Chemical Formulas 1-3.

[Preparation Example 5]:

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet pipe, 213.6 g of propylene glycol monomethyl ether acetate was placed, and the temperature was raised to 90° C. with stirring while replacing with nitrogen. Next, 30.0 g (0.30 moles) of methyl methacrylate, 11.0 g (0.05 moles) of tricyclodecyl methacrylate and 46.9 g (0.65 moles) of methacrylic acid were mixed with To the obtained monomer mixture, 4.0 g of t-butylperoxy-2-ethylhexanoate was added, and it was dropped into the aforementioned flask from a dropping funnel. After completion of dropping, the copolymer was produced by stirring at 95° C. for about 1 hour to carry out a copolymerization reaction. Next, after replacing the inside of the flask with air, 78.2 g (0.55 moles) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of hydroquinone (polymerization inhibitor) were added ), carry out ring-opening addition reaction at 120 ℃ for about 6 hours, manufacture copolymer. Next, 221.3 g of propylene glycol monomethyl ether was added to this reaction solution to obtain a copolymer solution (weight average molecular weight 6,400) having a solid content concentration of 30% by mass. The copolymer (photocurable resin E) prepared in Preparation Example 5 has the constituent units shown in the above Chemical Formulas 1-3.

[Preparation Example 6]:

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet pipe, 213.6 g of propylene glycol monomethyl ether acetate was placed, and the temperature was raised to 90° C. with stirring while replacing with nitrogen. Next, a mixture of 70.0 g (0.70 moles) of methyl methacrylate, 11.0 g (0.05 moles) of tricyclodecyl methacrylate and 18.1 g (0.25 moles) of methacrylic acid To the obtained monomer mixture, 4.0 g of t-butylperoxy-2-ethylhexanoate was added, and it was dropped into the aforementioned flask from a dropping funnel. After completion of dropping, the copolymer was produced by stirring at 95° C. for about 1 hour to carry out a copolymerization reaction. Next, after replacing the inside of the flask with air, 28.5 g (0.20 moles) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of hydroquinone (polymerization inhibitor) were added ), carried out ring-opening addition reaction at 120 DEG C for 8 hours, and produced copolymer. Next, 221.3 g of propylene glycol monomethyl ether was added to this reaction solution to obtain a copolymer solution (weight average molecular weight 6,500) having a solid content concentration of 30% by mass. The copolymer (photocurable resin-F) prepared in Preparation Example 6 has the structural unit shown in the above Chemical Formula 1-3.

[Preparation Example 7]:

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet pipe, 213.6 g of propylene glycol monomethyl ether acetate was placed, and the temperature was raised to 90° C. with stirring while replacing with nitrogen. Next, 30.0 g (0.30 moles) of methyl methacrylate, 11.0 g (0.05 moles) of tricyclodecyl methacrylate and 46.9 g (0.65 moles) of methacrylic acid were mixed with To the obtained monomer mixture, 4.0 g of t-butylperoxy-2-ethylhexanoate was added, and it was dropped into the aforementioned flask from a dropping funnel. After the dropping was completed, the copolymer was produced by stirring at 95° C. for about 3 hours to carry out a copolymerization reaction. Next, after replacing the inside of the flask with air, 49.8 g (0.35 moles) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of hydroquinone (polymerization inhibitor) were added ), at 120 ℃, carry out the ring-opening addition reaction for about 3 hours, manufacture copolymer. Next, 221.3 g of propylene glycol monomethyl ether was added to this reaction solution to obtain a copolymer solution (weight average molecular weight: 23,900) having a solid content concentration of 30% by mass. The copolymer (photocurable resin G) prepared in Preparation Example 7 has the constituent units shown in the above Chemical Formulas 1-3.

[Preparation Example 8]:

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet pipe, 213.6 g of propylene glycol monomethyl ether acetate was placed, and the temperature was raised to 90° C. with stirring while replacing with nitrogen. Next, 30.0 g (0.30 moles) of methyl methacrylate, 11.0 g (0.05 moles) of tricyclodecyl methacrylate and 46.9 g (0.65 moles) of methacrylic acid were mixed with To the obtained monomer mixture, 4.0 g of t-butylperoxy-2-ethylhexanoate was added, and it was dropped into the aforementioned flask from a dropping funnel. After the dropping was completed, the copolymer was produced by stirring at 95° C. for about 2 hours to carry out a copolymerization reaction. Next, after replacing the inside of the flask with air, 64.0 g (0.45 moles) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of hydroquinone (polymerization inhibitor) were added ), carry out ring-opening addition reaction at 120 ℃ for about 4 hours, manufacture copolymer. Next, 221.3 g of propylene glycol monomethyl ether was added to this reaction solution to obtain a copolymer solution (weight average molecular weight 17,800) having a solid content concentration of 30% by mass. The copolymer (photocurable resin H) prepared in Preparation Example 8 has the constituent units shown in the above Chemical Formulas 1-3.

Furthermore, the thermosetting resin I is a self-synthesized resin material, please refer to the following preparation examples 9-1 to 9-2. The thermosetting resin I-1 of the preparation example 9-1 and the thermosetting resin I-2 of the preparation example 9-2 can be used individually or in combination as the material of the thermosetting resin I.

[Preparation Example 9-1: Preparation of Thermosetting Resin I-1]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was allowed to flow to make it a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was put in and heated to 85°C while stirring. Next, 19 parts of methacrylic acid (for forming the structural unit on the lower left side) and acrylic acid 3,4-epoxytricyclo[5.2.1.02,6] were dropped into the flask using a dropping pump for about 5 hours. A mixture of decane-8-yl ester and 3,4-epoxytricyclo[5.2.1.02,6]decane-9-yl acrylate (the content ratio is 50:50 in molar ratio) (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) 171 parts were dissolved in 40 parts of propylene glycol monomethyl ether acetate. On the other hand, 26 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in propylene glycol monolayer was added dropwise to the flask using another dripping pump for about 5 hours. A solution of 120 parts of methyl ether acetate. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (thermosetting resin I-1) with a solid content of 43.5%. The weight average molecular weight of the obtained resin I-1 was 8000. The copolymer prepared in Preparation Example 9-1 has the constitutional unit shown in the following Chemical Formula 1-4. [Chemical formula 1-4]

[Preparation Example 9-2: Preparation of Thermosetting Resin I-2]

The flask equipped with a reflux condenser, a dropping funnel, and a stirrer was replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80° C. with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02]6)decane-9- 289 parts of propylene glycol monomethyl ether acetate and 125 parts of mixed solutions of propylene glycol monomethyl ether acetate were dripped over 5 hours to the mixture of acrylic acid ester (the content ratio was 1:1 in molar ratio). On the other hand, a solution in which 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition, the mixture was kept at 80° C. for 4 hours, and then cooled to room temperature to obtain a copolymer (thermosetting resin I-2) with a solid content of 35.1% and a viscosity of 125 mPas measured by a Brookfield viscometer (23° C.). solution. The weight average molecular weight (Mw) of the obtained copolymer was 9200. The copolymer prepared in Preparation Example 9-2 had structural units as shown in the following Chemical Formulas 1-5. [Chemical formula 1-5]

Thermosetting resin J is a self-synthesized resin material, please refer to the following preparation examples 10-1 to 10-2. The thermosetting resin J-1 of the preparation example 10-1 and the thermosetting resin J-2 of the preparation example 10-2 can be used as the material of the thermosetting resin J either individually or in combination.

[Preparation Example 10-1: Preparation of Thermosetting Resin J-1]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was allowed to flow to make it a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was placed, and heated to 85°C while stirring. Next, 19 parts of methacrylic acid (for forming the structural unit on the lower left side) and acrylic acid 3,4-epoxytricyclo[5.2.1.02,6] were dropped into the flask using a dropping pump for about 5 hours. A mixture of decane-8-yl ester and 3,4-epoxytricyclo[5.2.1.02,6]decane-9-yl acrylate (the content ratio is 50:50 in molar ratio) (trade name " E-DCPA", manufactured by Daicel Co., Ltd.) 171 parts were dissolved in 40 parts of propylene glycol monomethyl ether acetate. On the other hand, 26 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in propylene glycol monolayer was added dropwise to the flask using another dripping pump for about 5 hours. A solution of 120 parts of methyl ether acetate. After the drop of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 4.5 hours, and then cooled to room temperature to obtain a solution of the copolymer (thermosetting resin J-1) with a solid content of 43.5%. The weight average molecular weight of the obtained resin J-1 was 18,000. The copolymer prepared in Preparation Example 10-1 has the constituent units shown in the above Chemical Formula 1-4.

[Preparation Example 10-2: Preparation of Thermosetting Resin J-2]

The flask equipped with a reflux condenser, a dropping funnel, and a stirrer was replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80° C. with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02]6)decane-9- 289 parts of propylene glycol monomethyl ether acetate and 125 parts of mixed solutions of propylene glycol monomethyl ether acetate were dripped over 5 hours to the mixture of acrylic acid ester (the content ratio was 1:1 in molar ratio). On the other hand, a solution in which 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition, the mixture was kept at 80° C. for 6.5 hours, and then cooled to room temperature to obtain a copolymer (thermosetting resin J-2) with a solid content of 35.1% and a viscosity of 125 mPas measured by a Brookfield viscometer (23° C.). solution. The weight average molecular weight (Mw) of the obtained copolymer was 19,100. The copolymer prepared in Preparation Example 10-2 has the constituent units shown in the above Chemical Formulas 1-5.

Thermosetting resin K is a self-synthesized resin material, please refer to the following preparation examples 11-1~11-2. The thermosetting resin K-1 of the preparation example 11-1 and the thermosetting resin K-2 of the preparation example 11-2 can be used as the material of the thermosetting resin K either individually or in combination.

[Preparation Example 11-1: Preparation of Thermosetting Resin K-1]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was allowed to flow to make it a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was placed, and heated to 85°C while stirring. Next, 19 parts of methacrylic acid (for forming the structural unit on the lower left side) and acrylic acid 3,4-epoxytricyclo[5.2.1.02,6] were dropped into the flask using a dropping pump for about 5 hours. A mixture of decane-8-yl ester and 3,4-epoxytricyclo[5.2.1.02,6]decane-9-yl acrylate (the content ratio is 50:50 in molar ratio) (trade name " E-DCPA", manufactured by Daicel Co., Ltd.) 171 parts were dissolved in 40 parts of propylene glycol monomethyl ether acetate. On the other hand, 26 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in propylene glycol monolayer was added dropwise to the flask using another dripping pump for about 5 hours. A solution of 120 parts of methyl ether acetate. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 6 hours, and then cooled to room temperature to obtain a solution of a copolymer (thermosetting resin K-1) with a solid content of 43.5%. The weight average molecular weight of the obtained resin K-1 was 24,000. The copolymer prepared in Preparation Example 11-1 has the constituent units shown in the above Chemical Formula 1-4.

[Preparation Example 11-2: Preparation of Thermosetting Resin K-2]

The flask equipped with a reflux condenser, a dropping funnel, and a stirrer was replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80° C. with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.02,6]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02]6)decane-9- 289 parts of propylene glycol monomethyl ether acetate and 125 parts of mixed solutions of propylene glycol monomethyl ether acetate were dripped over 5 hours to the mixture of acrylic acid ester (the content ratio was 1:1 in molar ratio). On the other hand, a solution in which 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition, the mixture was kept at 80° C. for about 6 hours, and then cooled to room temperature to obtain a copolymer (thermosetting resin K-2) having a solid content of 35.1% and a viscosity of 125 mPas measured by a Brookfield viscometer (23° C.). ) solution. The weight average molecular weight (Mw) of the obtained copolymer was 25,400. The copolymer prepared in Preparation Example 11-2 had the constituent units shown in the above Chemical Formulas 1-5.

In view of the above, the embodiments of the present disclosure provide a colored resin composition, a photoresist structure formed by using the colored resin composition, and a color filter and a display device including the photoresist structure. In some embodiments, the colored resin composition includes a colorant, an alkali-soluble resin, a polymerizable unsaturated compound, a photopolymerization initiator, and a solvent, wherein the alkali-soluble resin includes a photocurable resin, and the weight of the photocurable resin is The average molecular weight (Mw) is lower than 20,000, and the titration acid value of potassium hydroxide (KOH) is lower than 100 mg/g. After the colored resin composition proposed in the embodiment is coated on the substrate and exposed to light, the composition of the alkali-soluble resin can significantly reduce the difference in the degree of cross-linking between the upper part of the composition far from the substrate and the lower part of the composition adjacent to the substrate. , thereby reducing the strength difference between the upper part and the lower part of the cross-linked composition. In particular, the appropriate combination of the molecular weight and acid value of the photocurable resin and/or thermosetting resin contained in the alkali-soluble resin proposed in some embodiments can obviously make the colored resin composition coated on the substrate to resist side etching on the top and bottom of the photoresist With the same force, after exposure and development, the formed photoresist structure can have a mushroom-shaped cross-section, and the undercut depth can be significantly reduced (for example, it can be reduced to about 1.0 μm or less than 1.0 μm). Therefore, according to the coloring resin composition proposed in the embodiments of the present application, the problem of photoresist peeling (peeling) can be avoided after the development process, and the photoresist structure as a whole and the outline of the edges have acceptable or good integrity. . Therefore, applying the display device of the embodiments of the present disclosure can avoid light exposure defects caused by the pixels of the display device due to partial detachment of the photoresist, and can also greatly improve the detection machine caused by the uneven light and dark lines caused by the defective photoresist. The problem of misjudging the number of photoresist defects is too high.

Although the present invention has been disclosed above with several preferred embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field can make any changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the appended patent application.

10, 20, 30, 40, 50, 60: substrate 11, 21, 31, 41, 51, 61: photoresist structure 21b: bottom surface 21c: arc line segment d ₀ , d: undercut depth A ₁ : vertical projection area A ₂ : Contact area L1 : Parallel line L2 : Vertical line U _C : Notch a,b,c: Point

FIG. 1A is a schematic cross-sectional view of a photoresist structure formed with a current colored resin composition. FIG. 1B is a top view of the photoresist structure formed with the current colored resin composition. FIG. 2A is a schematic cross-sectional view of a photoresist structure formed with the colored resin composition according to some embodiments of the present disclosure. FIG. 2B is a top view of a photoresist structure formed with the colored resin composition according to some embodiments of the present disclosure. Figures 3A to 3G are simple schematic diagrams of the film edge and undercut portion of the SEM images according to experiments 1-1 to 1-7, respectively. Figures 4A to 4G are simple schematic diagrams of the edge of the film layer and the undercut portion of the SEM images according to Experimental Examples 2-1 to 2-7, respectively. Figures 5A to 5C are simple schematic diagrams of the edge of the film layer and the undercut portion of the SEM images according to Experimental Examples 3-1 to 3-3, respectively. Figures 6A to 6C are simple schematic diagrams of the film edge and the undercut portion of the SEM images according to Experimental Examples 4-1 to 4-3, respectively.

20: Substrate

21: Photoresist structure

21b: Underside

21c: Arc segment

d: undercut depth

A ₁ : Vertical projection area

A ₂ : Contact area

L1: Parallel line

L2: vertical line

U _C : Notch

a,b,c: point

Claims (25)

A coloring resin composition comprising a colorant, an alkali-soluble resin, a polymerizable unsaturated compound, a photopolymerization initiator and a solvent, wherein the alkali-soluble resin comprises a photocurable resin, and the photocurable resin has a weight-average molecular weight of (Mw) is lower than 20000, and potassium hydroxide (KOH) titration acid value is less than 100 mg/g. The colored resin composition according to claim 1, wherein the potassium hydroxide (KOH) titration acid value of the photocurable resin is less than 55 mg/g. The colored resin composition according to claim 2, wherein the -COOH group contained in the photocurable resin accounts for 3.5%/mol to 31.2%/mol of the photocurable resin. The colored resin composition according to claim 1 or 2, wherein the weight-average molecular weight of the photocurable resin is between 6,000 and 20,000. The colored resin composition according to claim 4, wherein the -COOH group contained in the photocurable resin accounts for less than 7%/mol of the photocurable resin. The colored resin composition according to claim 1, wherein the ratio (Binder/Monomer Ratio) of the photocurable resin to the monomer of the polymerizable unsaturated compound is 6.7% to 300%. The colored resin composition as claimed in claim 1, wherein the photocurable resin of the alkali-soluble resin comprises a copolymer having a structure represented by the following formula (I):

Formula (I), wherein m, e, f, and g are positive integers. The colored resin composition according to claim 7, wherein, the structure shown in formula (I), wherein the entire molecular chain is set to be 100%, then m accounts for 1-10% of the polymer chain; e accounts for the polymer chain chain 20~70%; f accounts for 20~70% of the polymer chain; and g accounts for 1~35% of the polymer chain. The colored resin composition according to claim 7, wherein the copolymer of the structure represented by formula (I) comprises: Dicyclopentyl (meth)acrylate (TCDMA)/methyl (meth)acrylate (MMA)/glycidyl (meth)acrylate (GMA)/(meth)acrylic acid (MAA) the copolymer. The colored resin composition according to claim 9, wherein the main chain system of the copolymer of the structure represented by formula (I) comprises: (Meth) dicyclopentyl acrylate (TCDMA), which accounts for 3%/mol of the aforementioned main chain; Methyl (meth)acrylate (MMA), 70%/mol to 27%/mol of the aforementioned backbone; and Glycidyl (meth)acrylate (GMA), which accounts for 27%/mol to 70%/mol of the aforementioned main chain. The colored resin composition according to claim 1, wherein the alkali-soluble resin accounts for the range of 5 to 50 wt % of the colored resin composition, taking the total weight of the colored resin composition as 100 wt %. The colored resin composition according to claim 1, wherein the alkali-soluble resin may further comprise a thermosetting resin. The colored resin composition of claim 12, wherein the thermosetting resin accounts for 8.9% to 10% by weight of the colored resin composition, and the photocurable resin accounts for 1.5% to 17.4% by weight of the colored composition . The colored resin composition of claim 13, wherein the photocurable resin accounts for 1.5% to 14.6% by weight of the colored composition, and the potassium hydroxide (KOH) titration acid value is less than 50 mg/g. The colored resin composition according to claim 12, wherein the thermosetting resin has a weight-average molecular weight of 5,000 to 20,000, and a potassium hydroxide (KOH) titration acid value of 100 mg/g to 120 mg/g. The colored resin composition of claim 15, wherein the -COOH group contained in the thermosetting resin accounts for 18 mol% or less of the thermosetting resin. The colored resin composition according to claim 12, wherein the weight average molecular weight of the thermosetting resin is lower than 10,000. The colored resin composition as claimed in claim 1, wherein the total weight of the colored resin composition is 100% by weight, The colorant is in the range of 10% to 30% by weight of the colored resin composition; The polymerizable unsaturated compound is in the range of 5% by weight to 50% by weight of the colored resin composition; and The photopolymerization initiator is in the range of 0.1% by weight to 10% by weight of the colored resin composition. A photoresist structure, comprising the colored resin composition as described in any one of claims 1 to 18, coated on a substrate and formed after baking, exposing, and developing steps, wherein the photoresist structure is a convex and a vertical projected area of the protruding body on the substrate is greater than the contact area of a bottom surface of the protruding body and the substrate. The photoresist structure as claimed in claim 19, wherein the top of the protruding body has an arc, from a farthest point of an edge of the protruding body to the position where the bottom surface of the protruding body contacts the substrate A gap is formed between the system. The photoresist structure of claim 19, wherein a vertical projection of a farthest point of an edge of the convex body on the substrate has a distance from the position where the bottom surface of the convex body contacts the substrate, This distance is defined as an undercut depth, which is less than 1 μm. The photoresist structure of claim 21, wherein a parallel line is drawn parallel to the substrate at a highest vertex of the convex body, and a line is drawn perpendicular to the substrate at the farthest point of the edge of the convex body A vertical line, wherein the parallel line and the vertical line form an included angle equal to 90 degrees, and a section of the convex body includes an arc line segment between the parallel line and the vertical line. A color filter formed of the colored resin composition according to any one of claims 1 to 18. The color filter of claim 23 includes a photoresist layer, the photoresist layer is formed by applying the colored resin composition over a substrate and exposing and developing. A display device comprising the color filter as claimed in claim 23.

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