TWI770994B - Coloring resin composition, method of manufacturing the same, and method of manufacturing photoresist structure - Google Patents

Abstract

A coloring resin composition with a transmittance T% includes an initiator, a colorant, an alkali-soluble resin, a polymerizable unsaturated monomer, and a solvent. The initiator has a solid content S% and a light absorption A%. The light absorption, the solid content, the transmittance, and an illuminance E% of a mercury lamp comply the following equation: Σ _{(the initiator)}{ ∫ _360-460nm[light absorption of the initiator (A%)* transmittance of the coloring resin composition (T%)*illuminance (E%)]* solid content of the initiator}*10000 ≧20. The illuminance E% of the mercury lamp is 100 % when the mercury lamp emits 365 nm light.

Description

Colored resin composition, method for producing the same, and method for producing photoresist structure

The present disclosure relates to a composition, a method for manufacturing the same, and a method for manufacturing a photoresist structure, and more particularly, a coloring resin composition and a method for manufacturing the same and a method for manufacturing the photoresist structure.

Display devices have been widely used in daily life, including for various portable or non-portable electronic products, workplace equipment, smart home appliances, or vehicles. Photoresists play an important role in display devices. Taking a color liquid crystal display device as an example, a color filter is one of the means to make the display device full-color, thereby increasing its added value. The color filter generates three primary colors of red (R), green (G), and/or blue (B) by means of filtering, and then mixes the three primary colors in different intensity ratios to present various colors. The colored resin composition is the main raw material of the color filter. The color filter is made by coating a glass substrate with a colored resin composition of three colors of red, green, and/or blue (RGB) with a specific pattern.

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 full-profile light with smaller undercuts and full-profile Resistance structure, which is also one of the goals that the industry pays attention to and strives 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 profile.

Some embodiments of the present disclosure disclose a colored resin composition having a penetration value T%, which includes an initiator, a colorant, an alkali-soluble resin, a polymerizable unsaturated compound, and a solvent. The starter has a solids content of S% and an absorption value of A%. The relationship between the absorption value, the solid content, the penetration value and the light source illuminance E% of the mercury light source conforms to the following formula: Σ _{( Initiator )} { ∫ _360-460nm )*colored resin composition penetration value (T%)*light source illuminance (E%)]*solid content of initiator %}*10000≧20, where the light source illuminance E% is emitted when the mercury light source emits a wavelength of 365 nm. 100% in light time.

In some embodiments, the solids content of the initiator may range from 1.0 to 10.0% by weight.

In some embodiments, the colored resin composition may further include functional additives, wherein the content of the functional additives may be less than 1 wt % based on the total weight of the colored resin composition as 100 wt %.

In some embodiments, the alkali-soluble resin may comprise a photosetting resin, a thermosetting resin, or a combination thereof.

In some embodiments, based on the total weight of the colored resin composition as 100 wt %, the content of the alkali-soluble resin may range from 1 to 20 wt %.

In some embodiments, the polymerizable unsaturated compound may comprise a photopolymerizable monomer.

In some embodiments, based on the total weight of the colored resin composition as 100 wt %, the content of the polymerizable unsaturated compound may range from 10 to 30 wt %.

Some embodiments of the present disclosure disclose a method for manufacturing a colored resin composition, which includes: preparing an alkali-soluble resin; and mixing the alkali-soluble resin with a coloring agent, a polymerizable unsaturated compound, a solvent, and an initiator to obtain a colored resin composition. The initiator has an absorption value A% and a solid content S%, the colored resin composition has a penetration value T%, and the relationship between the absorption value, solid content, penetration value and the light source illuminance E% of the mercury light source is as follows Formula: Σ _{( Initiator )} { ∫ _360-460nm [Absorptivity of Initiator (A%)*Transmission Value of Colored Resin Composition (T%)*Light Source Illuminance (E%)]*Initiator of Solid content (S%) }*10000 ≧20, where the light source illuminance E% is 100% when the mercury light source emits light with a wavelength of 365 nm.

Some embodiments of the present disclosure disclose a method for manufacturing a photoresist structure, which includes: providing a substrate; forming a coating on the substrate, wherein the coating comprises the above-mentioned colored resin composition; and baking the coating at a temperature below 150° C. forming a photoresist layer; and exposing and developing the photoresist layer to form a photoresist structure.

In some embodiments, the photoresist structure is a convex body having a bottom surface contacting the substrate, a top surface opposite the bottom surface, and a top surface connecting the top surface and the bottom surface The side edge, when viewed from the cross-section of the convex body, the included angle between the side edge and the bottom surface is <95∘.

In some embodiments, the photoresist structure is a convex body, and the convex body has a bottom surface contacting the substrate and a top surface opposite to the bottom surface, wherein the area of the top surface≦the bottom surface area.

In some embodiments, the photoresist structure is a convex body, and the convex body has a bottom surface contacting the substrate and a top surface opposite to the bottom surface, and the projection of the top surface on the substrate has a The first projected edge and the projection of the bottom surface on the substrate has a second projected edge corresponding to the first projected edge, wherein there is an undercut depth between the first projected edge and the second projected edge, the bottom The depth of cut is less than or equal to 0 μm.

It will be further understood that when the terms "comprises", "comprising", "includes" and/or "including" are used in this specification, they refer specifically to the stated features The presence of components, integers, steps, operations, elements, components, and/or groups thereof, but does not preclude the presence or addition of one or more other characteristic components, integers, steps, operations, elements, components, and/or its group. When the singular forms "a (a)" and "an (an)" are used in this specification, they are also intended to include the plural forms unless the context clearly dictates otherwise.

Additionally, unless expressly stated otherwise, numerical values relating to a particular component should be construed as including a tolerance range in the interpretation of the component.

The expression "a-b" used herein to denote a particular numerical range is defined as "≥a and ≤b".

The photoresist composition is a compound sensitive to radiation, which mainly includes resin material, solvent, initiator and sensitizer. The resin material is used as a binder, and the solvent is a diluent liquid that can dissolve other materials/compounds. The photoresist composition is made in liquid form for ease of use. Generally, photoresist compositions can be classified into positive photoresist compositions and negative photoresist compositions. After the positive photoresist composition is exposed to light, the exposed part can be dissolved and removed by chemical substances (photoresist or developer), leaving the pattern of the unexposed part. The negative photoresist composition is opposite to the positive photoresist. After the negative photoresist composition is illuminated, the unexposed part can be dissolved and removed by chemical substances (photoresist removal agent or developer), leaving the pattern of the exposed part. The following description will be made by taking the negative photoresist composition as the photoresist material of some embodiments of the present disclosure.

In the manufacturing method of the photoresist structure, the traditional photoresist structure will cause the bottom of the photoresist due to the photoresist process, especially in the low temperature photoresist process where the process temperature is lower than the polymer glass transition temperature (Tg) after the photoresist is cured. As the transmittance of light decreases, the bottom sensitivity is insufficient, resulting in insufficient crosslinking at the bottom of the photoresist structure close to the substrate and a certain undercut depth. FIG. 1 is a schematic cross-sectional view of a photoresist structure 13 formed on a substrate 10 with a conventional colored resin composition. As shown in FIG. 1, the photoresist structure 13 has a bottom surface 13b in contact with the substrate 10, a top surface 13t opposite to the bottom surface 13b, and side edges 13s connecting the top surface 13t and the bottom surface 13b, wherein the side edges 13s There is an included angle α with the bottom surface 13b. As shown in FIG. 1, the area of the top surface 13t>the area of the bottom surface 13b, and the included angle α>90∘. Further, the projection of the top surface 13t on the substrate 10 has a first projected edge 13ts and the projection of the bottom surface 13b on the substrate 10 has a second projected edge 13bs. The first projected edge 13ts is separated from the second projected edge 13bs by a distance defined as the undercut depth d0. If the undercut depth d0 is too deep (too large), it is easy to cause photoresist peeling (Peeling) during the development process, which will expose the pixels of the display device, or produce uneven light and dark lines, which will cause the detector to misjudge the number of photoresist defects to be too high. .

In order to meet the above needs, the embodiments of the present disclosure propose a colored resin composition that can improve the problem of undercut too deep after the photoresist structure is formed by the traditional colored resin composition in the photoresist process, especially in the low temperature photoresist process. , a photoresist structure formed by using the colored resin composition and a method for forming the photoresist structure.

One aspect of the present disclosure relates to a colored resin composition, which includes an initiator, a colorant, an alkali-soluble resin, a polymerizable unsaturated compound, and a solvent. The starter has a solids content of S% and an absorption value of A%. The relationship between the absorption value, the solid content, the penetration value and the light source illuminance E% of a mercury light source conforms to the following formula: Σ _{( Initiator )} { ∫ _360-460nm %)*colored resin composition penetration value (T%)*light source illuminance (E%)]*solid content of initiator (S%) }*10000≧20, where the light source illuminance E% is at the wavelength emitted by the mercury light source 100% at 365 nm light.

The absorption value A% of the starting agent is obtained by dissolving the starting agent into propylene glycol monomethyl ether acetate (PGMEA) to make 0.001 wt%, then packing it into a quartz cell and putting it into UV/VIS Ultraviolet/visible light spectrometer is measured and obtained, and the penetration value T% of the colored resin composition is obtained by making the colored resin composition into a color chip, and then putting it into the UV/VIS ultraviolet/visible light spectrometer for measurement. . The illuminance of the light source (accumulation/per 1 sec normalization value) E% is measured by placing the spectrospectrometer under the mercury light source to obtain the spectrogram of the mercury light source. The illuminance at a wavelength of 365 nm of light in the spectrum was obtained by normalizing 100%.

Examples of the initiator are not particularly limited as long as it conforms to the above formula. By selecting an initiator that conforms to the above formula, the upper part (farther away from the substrate) and the lower part (closer to the substrate) of the photoresist layer formed by the colored resin composition on the substrate can have a lower degree of crosslinking. The difference in strength, in turn, narrows the difference in strength between the upper and lower parts of the composition after crosslinking. Accordingly, the upper part and the lower part of the photoresist layer formed after the colored resin composition of the present disclosure is coated on a substrate and subjected to an optical lithography process can have similar undercut resistance, and then the photoresist can be obtained after the development process. A photoresist structure with complete shape and no undercut defects. Examples of initiators may include, but are not limited to, oxime ester compounds, alkyl thioxanthone compounds, alkyl phenyl ketone compounds, bisimidazole compounds, triazine compounds, acyl phosphine oxide, benzoin compounds , Diphenyl ketone compounds, quinone compounds, 10-butyl-2-chloroacridone, benzyl, methyl phenylformate, acetophenone, titanocene compounds , and any combination thereof. In one embodiment, the initiator comprises at least one selected from the group consisting of: oxime ester compounds, alkyl thioxanthone compounds, alkyl phenyl ketone compounds, bisimidazole compounds, Acetophenone compounds, triazine compounds, acylphosphine oxide compounds, biimidazole compounds, and any combination thereof. In one embodiment, the initiator may be an oxime ester compound and an alkyl thioxanthone compound. In some embodiments, the solid content S% of the initiator ranges between 1.0 and 10.0% by weight, between 1.5 and 8.0%, or between 1.94 and 5.71% by weight.

In one embodiment, the alkali-soluble resin may include a photocurable resin, a thermoset resin, or a combination thereof. In some embodiments, the alkali-soluble resin is a binder. By including one or more alkali-soluble resins, the colored resin composition of the present disclosure can be smoothly attached to the surface of the substrate after exposure and development, and can effectively provide resistance against corrosion by acid, alkali or plasma.

In some embodiments, with the total weight of the colored resin composition being 100 wt %, the content of the alkali-soluble resin may be in the range of 1-20 wt %, 5-15 wt %, or 8-12 wt % between.

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, including 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 words in parentheses, for example, (meth)acrylate compounds, including acrylate compounds, and methacrylate compounds. The polymerizable unsaturated compound may also be referred to as a polymerizable compound.

In some embodiments, the polymerizable unsaturated compound may comprise a photopolymerizable monomer, which may include, but is not limited to, at least one selected from the group consisting of: nonylphenyl carbitol acrylate , 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and other polymerizable compounds with one ethylenically unsaturated bond ; 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate Polymerizable compounds having two ethylenically unsaturated bonds, such as esters, bis(acrylooxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate; and trimethylol Propane tri(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(meth)acrylate 2-(meth)acryloyloxyethyl) isocyanate, tetra(meth)acrylate ethylene glycol modified pentaerythritol, hexa(meth)acrylate ethylene glycol modified dipentaerythritol, tetra(meth)acrylic acid Propylene glycol-modified pentaerythritol, propylene glycol hexa(meth)acrylate-modified dipentaerythritol, tetra(meth)acrylate-caprolactone-modified pentaerythritol, hexa(meth)acrylate-modified dipentaerythritol, etc. have three A polymerizable compound with one ethylenically unsaturated bond; and any combination thereof. 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 includes a polymerizable compound having three ethylenically unsaturated double bonds. In one embodiment, the polymerizable unsaturated compound may include dipentaerythritol hexa(meth)acrylate.

In some embodiments, based on the total weight of the colored resin composition as 100 wt %, the content of the polymerizable unsaturated compound may range from 10 to 30 wt %, 15 to 25 wt %, or 18 to 22 wt % %between.

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 means containing -COO- in the molecule but not -O- containing solvent), ether solvent (here means a solvent containing -O- but not -COO- in the molecule), ether ester solvent (here means containing -COO- and -O in the molecule - solvent), ketone solvent (here means a solvent containing -CO- but not -COO- in the molecule), alcohol solvent (here means containing OH in the molecule but not -O-, -CO - and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and any combination thereof.

Examples of ester solvents may include, but are not limited to, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isobutyl acetate Amyl, Butyl Propionate, Isopropyl Butyrate, Ethyl Butyrate, Butyl Butyrate, Methyl Pyruvate, Ethyl Pyruvate, Propyl Pyruvate, Methyl Acetate, Ethyl Acetate , cyclohexanol acetate and γ-butyrolactone. Examples of ether solvents may include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Ethylene 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 Dibutyl alcohol, anisole, phenethyl ether and methyl anisole. Examples of ketone solvents may include, but are not limited to, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl- 2-pentanone, cyclopentanone, cyclohexanone (CHN) and isophorone. Examples of alcohol solvents may include, but are not limited to, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol. Examples of the aromatic hydrocarbon solvent may include, but are not limited to, benzene, toluene, xylene, 1,3,5-trimethylbenzene, and the like. Examples of amide solvents may include, but are not limited to, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

In some embodiments, from the aspect of coatability and drying, the solvent can be selected from propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, propylene glycol monomethyl ether, 3-ethoxypropionic acid Ethyl ester, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone, N , N-dimethylformamide, and any combination thereof. In one embodiment, the solvent may comprise propylene glycol monomethyl ether acetate.

In some embodiments, based on the total weight of the colored resin composition as 100 wt %, the content of the solvent may range from 3 to 95 wt %, 40 to 60 wt %, or 43 to 50 wt %. When the content of the solvent is in the above range, the flatness at the time of coating can be improved, thereby improving the display characteristics.

In some embodiments, the colorant of the colored resin composition may include pigments and dyes.

According to some embodiments, the pigments are not particularly limited, and organic pigments or any well-known pigments may be used, such as compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists). Examples of pigments may include, but are not limited to, C.I. Pigment Red R9, R97, R105, R122, R123, R144, R149, R166, R168, R175, R176, R177, R179, R180, R192, R209, R215, R216, R224, R242 , R254, R255, R264, R265; C.I. Pigment Yellow Y3, Y12, Y13, Y14, Y15, Y16, Y17, Y20, Y24, Y31, Y53, Y83, Y86, Y93, Y94, Y109, Y110, Y117, Y125, Y128, Y137, Y138, Y139, Y147, Y148, Y150, Y153, Y154, Y166, Y173, Y194, Y214; C.I. Pigment Blue B15, B15:3, B15:4, B15:6, B60, B80, B16; C.I. Pigment Orange O13, O31, O36, O38, O40, O42, O43, O51, O55, O59, O 61, O64, O65, O71, O73; C.I. Pigment Violet P1, P19, P23, P29, P32, P36, P38; C.I. Pigment Green G1, G2, G4, G7, G8, G10, G13, G14, G15, G17, G18, G19, G26, G36, G45, G48, G50, G51, G54, G55, G58, G59; or any of them combination.

According to some embodiments, the dye of the colorant is not particularly limited, and any well-known dye may be used, such as solvent dyes, acid dyes, direct dyes, mordant dyes, classified as pigments in the Color Index (published by The Society of Dyers and Colourists) Compounds other than those having a color tone, and/or well-known dyes described in the dyeing book (color dyeing company). Examples of dyes may include, but are not limited to, 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 phospholine dyes, nitro dyes, or any combination thereof.

In some embodiments, with the total weight of the coloring resin composition being 100 wt%, the content of the colorant may be in the range of 15-55 wt%, 20-55 wt%, or 22-53 wt% .

In one embodiment, the colored resin composition may further include functional additives. Examples of functional additives may include, but are not limited to, antioxidants, surfactants, leveling agents, fillers, photostabilizers, and chain transfer agents. When the colored resin composition contains functional additives, the content of the functional additives is less than 1 wt % based on the total weight of the colored resin composition being 100 wt %.

Another aspect of the present disclosure relates to a photoresist structure and a method for fabricating the same. The photoresist structure of the present disclosure can be formed through the above-mentioned colored resin composition by the method of manufacturing the photoresist structure of the present disclosure. The photoresist structure and the manufacturing method thereof of the present disclosure are further described below with reference to FIGS. 2-3D.

FIG. 2 is a flowchart illustrating a method 200 of fabricating a photoresist structure according to an embodiment of the present disclosure. FIGS. 3A to 3D are schematic cross-sectional views illustrating various steps of the method 200 for fabricating a photoresist structure according to an embodiment of the present disclosure.

Referring to FIG. 2 and FIG. 3A simultaneously, the manufacturing method 200 provides the substrate 20 in step S201. The material used to form the substrate 20 is not particularly limited. Examples of substrates may include, but are not limited to, silicon substrates, metal substrates, glass substrates, polyimide substrates, or sapphire substrates. Step S201 may include performing a cleaning process on the substrate 20 to remove impurities on the substrate 20, thereby increasing the adhesion between the substrate 20 and the coating layer formed thereon, and avoiding defects or peeling of the finally obtained photoresist structure. Phenomenon.

Next, referring to FIG. 2 and FIG. 3B , the coating layer 21 including the above-mentioned colored resin composition is formed on the substrate 20 in step S203 . Coating 21 may be formed on substrate 20 using any method. The method for forming the coating layer 21 is not particularly limited, and examples thereof may include, but are not limited to, an inkjet process, a coating process, a transfer process, or a screen printing process.

Next, referring to FIG. 2 and FIG. 3C, in step S205, the coating layer 21 is baked at a temperature below 150°C to form a photoresist layer 23'. In some embodiments, the polymer glass transition temperature (Tg) of the photoresist layer 23' is higher than or equal to 150°C. In one embodiment, the polymer glass transition temperature (Tg) of the photoresist layer 23' is between 150°C and 150°C. 200°C, but the present disclosure is not limited thereto.

Next, referring to FIG. 2 and FIG. 3D , exposure and development processes are performed in step S207 to form the photoresist structure 23 . As shown in FIG. 3D, the photoresist structure 23 has a bottom surface 23b in contact with the substrate 20, a top surface 23t opposite to the bottom surface 23b, and side edges 23s connecting the top surface 23t and the bottom surface 23b, wherein the side edges 23s is an arc line segment. In some embodiments, the area of the top surface 23t≦the area of the bottom surface 23b. In some embodiments, there is an included angle α between the side edge 23s and the bottom surface 23b. In some embodiments, α<95∘, and in further embodiments, α≦90∘.

The projection of the top surface 23t on the substrate 20 has a first projected edge 23ts and the projection of the bottom surface 23b on the substrate 20 has a second projected edge 23bs. The first projected edge 23ts and the second projected edge 23bs are subtracted to obtain a distance, which is defined as the undercut depth d0. When the value of the first projected edge 23ts is less than or equal to the value of the second projected edge 23bs as shown in Figure 3D, that is, when the first projected edge 23ts minus the second projected edge 23tb is less than or equal to 0 μm, it is determined that there is no undercut depth d0.

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 examples and comparative examples is given below, and the colored resin compositions in these examples are used to form photoresists. After the structure, several tests, analyses and evaluations are performed to observe the characteristics of the photoresist structure fabricated from the colored resin composition according to the embodiment of the present disclosure.

The following are commercially available products such as NCI-730 (manufactured by ADEKA Co., Ltd.), PBG-345, PBG-346 and PBG-327 (manufactured by Changzhou Qiangqi Electronic New Material Co., Ltd.) and DETX (manufactured by Nippon Kayaku Co., Ltd.) Starter; propylene glycol monomethyl ether acetate (PGMEA) as solvent; dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) as polymerizable unsaturated compound; 4,4'- Butyl-bis(6-tert-butyl-m-cresol) (BBM-S) was used as antioxidant; experiments were carried out with the following alkali-soluble resin A, alkali-soluble resin B, alkali-soluble resin C or a combination thereof and a colorant. These experimental contents can specifically illustrate the effects that can be achieved by the colored resin composition according to the embodiments of the present disclosure. However, the following examples and comparative examples are for illustrative purposes only, and should not be construed as limitations on the implementation of the present disclosure.

1. Preparation of Alkali-Soluble Resin A

(1) Preparation of alkali-soluble resin A

After placing 213.6 g of propylene glycol monomethyl ether acetate in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas introduction pipe, nitrogen was introduced through the gas introduction pipe to replace the air in the flask. While stirring propylene glycol monomethyl ether acetate, the temperature of propylene glycol monomethyl ether acetate was raised to 90°C. Next, in a monolith containing 70.0 g (0.70 mol) of methyl methacrylate, 11.0 g (0.05 mol) of tricyclodecyl methacrylate and 18.1 g (0.25 mol) of methacrylic acid To the bulk mixture was added 4.0 g of t-butylperoxy-2-ethylhexanoate to form a mixture. The above mixture was dropped into the above flask through a funnel. After the completion of dropping, the copolymerization reaction was carried out by stirring at 95° C. for about 1 hour. Next, after replacing the nitrogen in the above-mentioned flask with air, 28.5 g (0.20 mol) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of hydroquinone (polymerization) were added. Inhibitor), a ring-opening addition reaction was carried out at 120 ° C for 8 hours, thereby producing a copolymer. Finally, 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 weight as the alkali-soluble resin A.

(2) Preparation of Alkali-Soluble Resin B

After placing 213.6 g of propylene glycol monomethyl ether acetate in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas introduction pipe, nitrogen was introduced through the gas introduction pipe to replace the air in the flask. While stirring propylene glycol monomethyl ether acetate, the temperature of propylene glycol monomethyl ether acetate was raised to 90°C. Next, in a monomer mixture containing 15.0 g (0.10 mol) of benzyl methacrylate, 93.0 g (0.55 mol) of cyclohexyl methacrylate and 25.3 g (0.35 mol) of methacrylic acid 4.0 g of t-butylperoxy-2-ethylhexanoate was added to form a mixture. The above mixture was dropped into the above flask through a funnel. After the dropping was completed, the copolymerization reaction was carried out by stirring at 95° C. for about 2 hours. Next, after replacing the nitrogen in the above-mentioned flask with air, 28.5 g (0.20 mol) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst) and 0.6 g of hydroquinone (polymerization) were added. Inhibitor), carry out a ring-opening addition reaction at 120° C. for about 7 hours, thereby producing a copolymer. Finally, 221.3 g of propylene glycol monomethyl ether was added to this reaction solution to obtain a copolymer solution (weight average molecular weight 17,000) having a solid content concentration of 33% by weight as the alkali-soluble resin B.

(3) Preparation of alkali-soluble resin C

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was allowed to flow into a nitrogen atmosphere, and 100 parts by weight of propylene glycol monomethyl ether acetate was placed, and while stirring, propylene glycol monomethyl ether ethyl was added. The acid ester was heated to 85°C. Next, 19 parts by weight of methacrylic acid and 171 parts by weight of acrylic acid 3,4-epoxytricyclo[5.2.1.02,6]decane dissolved in 40 parts by weight of propylene glycol monomethyl ether acetate were mixed A mixture of -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- A solution of DCPA", manufactured by Daicel Co., Ltd.) was dripped into the flask using a drip pump for about 5 hours. On the other hand, a solution containing 26 parts by weight of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 120 parts by weight of propylene glycol monomethyl ether acetate The flask was dripped into the flask over about 5 hours using another drip pump. After the drop of the solution containing the polymerization initiator was completed, the same temperature was maintained for about 3 hours, and then it was cooled to room temperature to obtain a copolymer with a solid content of 30% by weight (weight average molecular weight: 11,000) as an alkali-soluble resin C.

2. Preparation of colored resin composition

The coloring resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were prepared with the compositions and weight percentages shown in Tables 1 to 3 below. Table 1 Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Colorant: B15:6 23 wt% Alkali Soluble Resin A 10 wt% polymerizable unsaturated compound 20 wt% solvent 45 wt% starter 2 wt% Antioxidants <0.1 wt% Table 2 Example 2 Example 3 Example 4 Comparative Example 4 Colorant: B15:6 23 wt% Alkali Soluble Resin A 10 wt% - 10 wt% 10 wt% Alkali Soluble Resin B - 10 wt% - - polymerizable unsaturated compound 20 wt% 20 wt% 20 wt% 20 wt% solvent 41 wt% 41 wt% 44 wt% 44 wt% starter 6 wt% 6 wt% 3 wt% 3 wt% Antioxidants <0.1 wt% table 3 Example 5 Example 6 Colorant: R179 23 wt% Alkali Soluble Resin C 3 wt% - Alkali Soluble Resin A 7 wt% 10 wt% polymerizable unsaturated compound 20 wt% 20 wt% solvent 41 wt% 41 wt% starter 6 wt% 6 wt% Antioxidants <0.1 wt%

3. Evaluation of Colored Resin Compositions

(1) The initiators used in Examples 1 to 6 and Comparative Examples 1 to 4 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to make 0.001 wt%, respectively, and then placed in a quartz cell and placed into a UV/VIS ultraviolet/visible spectrometer (model: uv-2600 shimadzu) to obtain the absorption value (A%) of each initiator in Examples 1-6 and Comparative Examples 1-4, respectively.

(2) After the colored resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were made into color chips, respectively, Examples 1 to 6 and Comparative Example 1 were measured with an ultraviolet-visible light spectrometer (model: uv-2600 shimadzu). The penetration value T% of the colored resin composition of ~4. The light source illuminance of the light source was measured with a spectrometer (model: Ocean Optics USB2000+), and the light source illuminance E% was obtained by normalizing the wavelength illuminance when the wavelength of the light emitted by the mercury light source was 365 nm as 100%.

(3) Integrate the measured absorption value A% of the initiator, the penetration value T% of the colored resin composition and the light source illuminance E%, and use the initiator used in each example and the comparative example by weight The X value _of the _{colored resin} compositions _of Examples 1 to 6 and Comparative Examples 1 to 4 was calculated by adding the solid content of *Transmission value of colored resin composition (T%)*Light source illuminance (E%)]*Solid content of initiator (S%)}*10000 = X

The solid content of the initiators of Examples 1 to 6 and Comparative Examples 1 to 4, the integral calculated from the above results and the X value are listed in the following Tables 4 to 6 Table 4 starter Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Initiator ((A%) * Transmission value (T%) * Integrated value of light source illuminance (E%) (360-460nm) PBG-345 4.89E-04 PBG-346 2.67E-03 PBG-327 0.00E+00 NCI-730 5.63E-04 Starter solid content PBG-345 1.62% PBG-346 1.62% PBG-327 1.62% NCI-730 1.62% X value 26.70 4.89 5.63 0.00 table 5 starter Example 2 Example 3 Example 4 Comparative Example 4 Initiator ((A%) * Transmission value (T%) * Integrated value of light source illuminance (E%) (360-460nm) PBG-345 3.02E-02 3.02E-02 DETX 6.81E-02 9.94E-02 9.94E-02 6.81E-02 PBG-327 1.62E-02 NCI-730 - 6.57E-02 - Starter solid content PBG-345 0.85% 0.30% DETX 4.86% 4.50% 1.36% 2.43% PBG-327 1.93% NCI-730 - 1.36% - X value 44.37 47.83 22.44 17.44 Table 6 starter Example 5 Example 6 Initiator ((A%) * Transmission value (T%) * Integrated value of light source illuminance (E%) (360-460nm) PBG-345 4.23E-01 DETX 3.01E-01 PBG-327 5.87E-02 Starter solid content PBG-345 0.65% DETX 1.29% PBG-327 3.60% X value 48.02 21.12

4. Fabrication of the photoresist structure

(1) The colored resin compositions of Examples 1 to 6 and Comparative Examples 1 to 4 were respectively coated on glass substrates having a thickness of about 0.4 mm to about 0.7 mm by spin coating.

(2) The glass substrate coated with the colored resin composition is placed on a hot plate at about 80° C. to 90° C., and prebaking is performed for about 120 seconds.

(3) After the glass substrate is cooled, use an exposure machine to perform the exposure step, and then move the glass substrate to a developing machine to perform the development step to form the photoresist structures of Examples 1-6 and Comparative Examples 1-4 on the glass substrate.

5. Evaluation of photoresist structure

The photoresist structures of each example and the comparative example were photographed with a scanning electron microscope (SEM) (model: Hitachi SU3500), and the cross-sectional shapes, undercut depths and sides of the photoresist structures were observed and measured The angle between the edge and the bottom surface. SEM images of the photoresist structures of Examples 1 to 6 and Comparative Examples 1 to 4 are shown in FIGS. 4 to 13, respectively.

FIGS. 4 to 13 are SEM images of photoresist structures according to examples of the present disclosure and comparative examples. Figure 4 is the SEM image of the photoresist structure of Example 1; Figure 5 is the SEM image of the photoresist structure of Comparative Example 1; Figure 6 is the SEM image of the photoresist structure of Comparative Example 2; Figure 7 is the comparative example 3 is the SEM image of the photoresist structure; Figure 8 is the SEM image of the photoresist structure of Example 2; Figure 9 is the SEM image of the photoresist structure of Example 3; Figure 10 is the SEM image of the photoresist structure of Example 4 ; Figure 11 is the SEM image of the photoresist structure of Comparative Example 4; Figure 12 is the SEM image of the photoresist structure of Example 5; and Figure 13 is the SEM image of the photoresist structure of Example 6.

According to the SEM images of the photoresist structures of Examples 1 to 6 and Comparative Examples 1 to 4, the thickness of the photoresist structure, the angle between the side edge and the bottom surface, and the undercut depth were measured, and the measured undercut depth and side were measured. The angle between the edge and the bottom surface The photoresist structures of Examples 1-6 and Comparative Examples 1-4 were evaluated.

When the undercut depth d0 > 0 μm, it was evaluated as X, and when the angle between the side edge and the bottom surface was ≦90∘, it was evaluated as ⊚. For the definition of the undercut depth, please refer to the above-mentioned description of the undercut depth d0 of the photoresist structures 13 and 23 as shown in FIG. 1 and FIG. 3D, and for the definition of the angle between the side edge and the bottom surface, please refer to the above As shown in Figure 1 and Figure 3D, the description of the included angle α. The thickness, undercut depth, X value, and evaluation of the photoresist structures of Examples 1 to 6 and Comparative Examples 1 to 4 are shown in Tables 7 to 9 below. Table 7 Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Thickness (μm) 2.2 2.4 2.4 2.4 X value 26.70 4.89 0.00 0.00 Undercut depth -1.4□μm 2.1μm 1.5μm 5.6μm determination ◎ X X X Table 8 Example 4 Example 5 Example 6 Comparative Example 4 Thickness (μm) 2.4 2.2 2.2 2.4 X value 44.37 47.83 22.44 17.44 Undercut depth 0□μm -0.1μm -0.2μm 1.2μm determination ◎ ◎ ◎ X Table 9 Example 5 Example 6 Thickness (μm) 2.4 2.2 X value 48.02 21.12 Undercut depth 0μm -11.3μm determination ◎ ◎

From the results shown in Tables 7 to 9 above, it can be seen that when the X value calculated by the above formula of the colored resin composition is ≧ 20, the photoresist structure formed by using it has a complete shape and no undercut too deep defects. . Therefore, the overall and edge profiles of the photoresist structure formed by the colored resin composition proposed in the embodiments of the present disclosure have acceptable or good integrity. Therefore, the display device having the photoresist structure of the embodiment 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 uneven light and dark lines caused by the defective photoresist. The problem that the detector misjudges that the number of photoresist defects is too high.

The above-mentioned embodiments are only for illustrative purposes, and do not limit the scope of protection of the present disclosure. Other features, elements, methods, and parameters may be used to implement the present disclosure. 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.

10,20: Substrate 13,23: Photoresist structure 13t, 23t: top surface 13b, 23b: Bottom surface 13s, 23s: side edge 13bs, 23bs: Second projected edge 13ts,23ts: First projected edge 21: Coating 23': photoresist layer 200: Manufacturing Method S201~S207: Steps d0: Undercut depth

FIG. 1 is a schematic cross-sectional view of a photoresist structure formed on a substrate with a conventional colored resin composition. FIG. 2 is a flowchart illustrating a method for fabricating a photoresist structure according to an embodiment of the present disclosure. FIGS. 3A to 3D are schematic cross-sectional views illustrating various steps of a method for manufacturing a photoresist structure according to an embodiment of the present disclosure. FIGS. 4 to 13 are SEM images of photoresist structures according to examples of the present disclosure and comparative examples.

20: Substrate

23: Photoresist structure

23t: top surface

23b: Bottom surface

23s: side edge

23bs: Second projected edge

23ts: First projected edge

Claims (8)

A colored resin composition having a penetration value T%, the colored resin composition comprising: an initiator with an absorption value A% and a solid content S%; a colorant; an alkali-soluble resin; a polymerization Sexually unsaturated compound; and a solvent, wherein the relationship between the absorption value, the solid content, the transmission value and a light source illuminance E% of a mercury lamp light source conforms to the following formula: Σ _{(initial agent)} {ʃ _{360 -460nm} [absorption value of initiator (A%)*transmission value of colored resin composition (T%)*illuminance of light source (E%)]*solid content of initiator (S%)}*10000≧20 , wherein the illuminance E% of the light source is 100% when the mercury light source emits light with a wavelength of 365 nm, the range of the solid content S% is between 1.0 and 10.0% by weight, and the total amount of the colored resin composition is The weight is 100wt%, the content range of the alkali-soluble resin is between 1~20wt%, the content range of the polymerizable unsaturated compound is between 10~30wt%, the content range of the solvent is between 3~95wt%, And the content of the colorant ranges from 15 to 55 wt %. The colored resin composition of claim 1, wherein the alkali-soluble resin comprises a photosetting resin, a thermosetting resin, or a combination thereof. The colored resin composition of claim 1, wherein the polymerizable unsaturated and compounds containing photopolymerizable monomers. A method for producing a colored resin composition, comprising: preparing an alkali-soluble resin; and mixing the alkali-soluble resin with a colorant, a polymerizable unsaturated compound, a solvent and an initiator to obtain a colored resin composition , wherein the initiator has an absorption value A% and a solid content S%, the colored resin composition has a penetration value T%, and the absorption value, the solid content, the penetration value and a mercury lamp light source The relationship between the illuminance E% of a light source conforms to the following formula: Σ _(initiator) {ʃ _360-460nm [absorption value of initiator (A%) * transmission value of colored resin composition (T%)* Light source illuminance (E%)] * solid content of initiator (S%)}*10000≧20, wherein the light source illuminance E% is 100% when the mercury light source emits light with a wavelength of 365nm, and the solid content S The range of % is between 1.0 and 10.0% by weight, and the total weight of the colored resin composition is 100% by weight, the content of the alkali-soluble resin is between 1 and 20% by weight, and the content of the polymerizable unsaturated compound is 100% by weight. The content ranges from 10 to 30 wt %, the solvent content ranges from 3 to 95 wt %, and the colorant content ranges from 15 to 55 wt %. A method for manufacturing a photoresist structure, comprising: providing a substrate; forming a coating on the substrate, wherein the coating comprises the colored resin composition according to any one of claims 1 to 3; The coating is baked at the following temperature to form a photoresist layer; and The photoresist layer is exposed and developed to form a photoresist structure. The method for manufacturing a photoresist structure of claim 5, wherein the photoresist structure is a convex body, and the convex body has a bottom surface contacting the substrate, a top surface opposite to the bottom surface, and connecting the top surface One side edge of the surface and the bottom surface, when viewed from the cross section of the convex body, the included angle between the side edge and the bottom surface is <95°. The method for manufacturing a photoresist structure according to claim 5, wherein the photoresist structure is a convex body, and the convex body has a bottom surface contacting the substrate and a top surface opposite to the bottom surface, wherein the top surface The area of the surface ≦ the area of the bottom surface. The method for manufacturing a photoresist structure of claim 5, wherein the photoresist structure is a convex body, and the convex body has a bottom surface contacting the substrate and a top surface opposite to the bottom surface, the top surface The projection on the substrate has a first projected edge and the projection of the bottom surface on the substrate has a second projected edge corresponding to the first projected edge, wherein the first projected edge and the second projected edge There is an undercut depth between them, and the undercut depth is less than or equal to 0 μm.

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