阅读说明：本技术 一种感光树脂组合物和遮光间隔物 (Photosensitive resin composition and shading spacer ) 是由 钱园 徐锦标 黄智� 于 2020-04-27 设计创作，主要内容包括：本发明公开了一种感光树脂组合物和遮光间隔物,感光树脂组合物包括以下原料：甲基丙烯酸共聚物(A)、碱溶性树脂(B)、光可聚合化合物(C)、光聚合引发剂(D)、遮光剂(E),本发明制备工艺简单,能够形成遮光性高、与基板密合性优异的图案的感光树脂组合物,以及使用其形成的遮光间隔物。(The invention discloses a photosensitive resin composition and a shading spacer, wherein the photosensitive resin composition comprises the following raw materials: the present invention relates to a photosensitive resin composition which is capable of forming a pattern having high light-shielding properties and excellent adhesion to a substrate, and a light-shielding spacer formed using the same, and which is prepared by a simple process.)

1. A photosensitive resin composition and a light shielding spacer, characterized in that: the photosensitive resin composition comprises the following raw materials: a methacrylic acid copolymer (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a light-shading agent (E).

2. The photosensitive resin composition and the light shielding spacer according to claim 1, wherein: the alkali-soluble resin (B) has the following structural formula B:

wherein R1 is selected from any one of C1-C10 straight chain alkyl and C3-C10 branched chain alkyl; r2 and R3 each independently represent a substituent, and n is an integer of 1 to 10

Further R2 is selected from Any one of

Further R3 is selected fromAny one of

And the above is the position of the bond of the substituent group.

3. A photosensitive resin composition and a light-shielding spacer for realizing the above object according to claim 1 or 2, wherein: the preparation process comprises the following steps:

A. supplying a photosensitive composition solution onto a substrate to be provided with a light-shielding spacer in a film or pattern form by a method such as coating, and drying the solvent;

B. then, pattern formation is performed by a method such as photolithography for performing exposure and development;

C. then, additional exposure or thermal curing treatment is performed as necessary, thereby forming light-shielding spacers on the substrate.

Technical Field

The present invention relates to a photosensitive resin composition and a light shielding spacer.

Background

In L CD, a gap portion of about 1um to 10um is provided between a color filter and an electrode substrate such as a TFT substrate, and the gap portion is filled with a liquid crystal compound and sealed at its periphery with a sealing material, and in order to keep a cell gap between the color filter and the electrode substrate constant and uniform, particles having a constant particle diameter are dispersed in the gap portion as spacers, or columnar or stripe spacers having the same height as the cell gap are formed.

Conventionally, when a spacer having no light-shielding property is used for the TFT L CD, a TFT as a switching element may malfunction due to light transmitted through the spacer, and patent document 1 describes a method of using a spacer having a light-shielding property to prevent this.

In recent years, along with the change in panel structure, a method of forming light-shielding spacers having different heights at a time by photolithography has been proposed. Patent document 2 discloses: by controlling the exposure amount and the residual film ratio, the shape and the height difference of the spacers having different heights can be realized. Patent document 3 discloses a technique of using a plurality of organic coloring pigments as pigments, and patent document 4 discloses a technique of using an organic black pigment;

Disclosure of Invention

An object of the present invention is to provide a photosensitive resin composition and a light-shielding spacer to solve the problems set forth in the background art described above.

In order to achieve the purpose, the invention provides the following technical scheme: a photosensitive resin composition and a light shielding spacer, characterized in that: a methacrylic acid copolymer (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a light-shading agent (E).

Preferably, (B) is an alkali soluble resin having the following structural formula B:

structural formula B

Wherein:

r1 is selected from any one of C1-C10 straight-chain alkyl and C3-C10 branched-chain alkyl; r2 and R3 each independently represents a substituent group

Further R2 is selected from Any one of

Further R3 is selected fromAny one of

Position of bond of substituent group

Further, the present invention provides a light-shielding spacer formed using the above photosensitive resin composition

The invention has the following effects: according to the present invention, a photosensitive resin composition capable of forming a pattern having high light-shielding properties and excellent adhesion to a substrate, and a light-shielding spacer formed using the same can be provided.

Preferably, the preparation process comprises the following steps:

A. supplying a photosensitive composition solution onto a substrate to be provided with a light-shielding spacer in a film or pattern form by a method such as coating, and drying the solvent;

B. then, pattern formation is performed by a method such as photolithography for performing exposure and development;

C. then, additional exposure or thermal curing treatment is performed as necessary, thereby forming light-shielding spacers on the substrate.

Compared with the prior art, the invention has the beneficial effects that: the invention provides a photosensitive resin composition which has simple preparation process and can form a pattern with high light-shielding performance and excellent adhesion with a substrate, and a light-shielding spacer formed by using the photosensitive resin composition.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The photosensitive resin composition of the present invention comprises:

(A) methacrylic acid copolymer

(B) Alkali soluble resin

(C) Photopolymerizable compounds

(D) Photopolymerization initiator

(E) Light-shading agent

Hereinafter, each component of the photosensitive resin composition will be specifically described.

Methacrylic acid copolymer

The methacrylic acid copolymer used in the present invention has the following structural formula A

Wherein a, b, c and d are respectively independent integers of 1-50

The photosensitive resin composition contains the polymer. The methacrylic copolymer (A) has a weight average molecular weight (Mw) of 1000 to 30000, preferably 3000 to 20000, and an acid value of 40 to 180mgKOH/g, preferably 70 to 130 mgKOH/g. Within this range, the adhesion to the substrate is good, the photospeed is high, the crosslinking density is high, and the resolution is high.

The methacrylic copolymer is used in an amount of 1 to 30% by weight, preferably 5 to 20% by weight, based on the total weight of the solid content of the photosensitive resin composition (i.e., excluding the weight of the solvent). Within this range, the pattern after development is more excellent, and the adhesion of the cured film to the substrate is improved.

The methacrylic acid copolymer can be prepared by a known method, and the synthetic reaction scheme is as follows:

alkali soluble resin

The alkali-soluble resin used in the invention is a multifunctional ethylenic unsaturated compound containing a fluorene structure, and the structural formula B of the alkali-soluble resin is as follows:

wherein R1 is selected from any one of C1-C10 straight chain alkyl and C3-C10 branched chain alkyl; r2 and R3 each independently represent a substituent, and n is an integer of 1 to 10

Further R2 is selected from Any one of

Further R3 is selected fromAny one of

Position of bond of substituent group

The photosensitive resin composition contains the compound. The weight average molecular weight (Mw) of the alkali-soluble resin (B) is 1,000 to 20000, preferably 3,000 to 7,000. Within this range, the pattern development of the lower portion of the cured film is excellent.

The amount of the alkali-soluble resin is 5 to 50 wt%, preferably 10 to 30 wt%, based on the total weight of the solid content of the photosensitive resin composition (i.e., excluding the weight of the solvent). Within this range, the pattern can be developed with excellent adhesion to the substrate.

The reaction scheme for alkali-soluble resin synthesis is as follows:

the reaction scheme is as follows:

in the reaction equation 1, L1 is halogen, R1 is selected from any one of C1-C10 straight-chain alkyl and C3-C10 branched-chain alkyl, R2 and R3 independently represent substituent groups, n is an integer of 1-10Is selected from Any one of

Further, the method comprisesSelected from maleic anhydrideItaconic anhydrideCitraconic anhydrideAny one of

The ethylenically unsaturated double bond can improve the photosensitivity, curing effect, etc. of the resin composition, and the fluorene structure can improve the adhesion, alkali resistance, workability, strength, etc. of the cured material to the substrate. Further, after removing the uncured portions at the time of development, an image having a fine resolution can be formed in the pattern.

Photopolymerizable compounds

The photopolymerizable compound used in the invention may be any compound that can be polymerized by the activity of a polymerization initiator, and may be a polyfunctional monomer, oligomer or polymer that is commonly used for preparing a colored photosensitive resin composition. More preferably, the polymerizable compound may include a mono-functional or multi-functional ester compound of acrylic acid or methacrylic acid having at least one ethylenically unsaturated double bond, and may preferably include a multi-functional compound having at least two functional groups in view of chemical resistance.

The polymerizable compound may be selected from the group consisting of: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, a monoester of pentaerythritol tri (meth) acrylate and succinic acid, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, a monoester of dipentaerythritol penta (meth) acrylate and succinic acid, caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate (pentaerythritol triacrylate and hexamethylene diisocyanate) The reactants of (a), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, bisphenol a epoxy acrylate, and ethylene glycol monomethyl ether acrylate, and mixtures thereof, but is not limited thereto.

The amount of the photopolymerizable compound may be 5 to 60 wt%, or 10 to 45 wt%, based on the total weight of the solid content (i.e., excluding the weight of the solvent) of the photosensitive resin composition. If the amount of the photopolymerizable compound is within the above range, the pattern can be easily developed, because it is possible to prevent problems that the development time is prolonged and thus the process and residues are affected, to improve properties such as chemical resistance and elastic restoring force, and to prevent the pattern resolution from being deteriorated

Photopolymerization initiator

The photopolymerization initiator used in the present invention may be any known polymerization initiator.

Specific examples of the photopolymerization initiator (D) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1- [4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propanone, 1- (4-cumyl) -2-hydroxy-2-methyl-1-propanone, 1- (4-dodecylphenyl) -2-hydroxy-2-methyl-1-propanone, 2-dimethoxy-1, 2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl ] ethanone, O-1- [6- (pyrrol-2-ylcarbonyl) -9-ethyl-9H-carbazol-3-yl ] acetoxime, O-chloro-2- [4- (2-chloro-2-propyl) -1- (4-chloro-2-chloro-2-ethyl-2-phenyl-1-propanone, 2-methyl-1-methyl-1-propanone, 1-2-hydroxy-2-methyl-1-propanone, 1-2-1-propanone, 1-2-dimethoxy-1-propanone, 2-dimethoxy-1-dimethoxy-1-dimethoxy-1-dimethoxy-1-2, 2-1-dimethoxy-1-dimethoxy-2-1-2-dimethoxy-1-dimethoxy-2, 2-dimethoxy-1-dimethoxy-1-2, 2-1-dimethoxy-1-2, 2-dimethoxy-2, 2-dimethoxy-2, 2-dimethoxy-2-dimethoxy-methoxy-dimethoxy-1-dimethoxy-1-2, 2-methoxy-2-dimethoxy-1-2-dimethoxy-methoxy-2-dimethoxy-2-dimethoxy-2-dimethoxy-2-1-dimethoxy-methoxy-2-1-2-methoxy-2-methoxy-2-methoxy-2-methoxy-2-1-2-1-2-methoxy-2-1-methoxy-2-1-2-1-2-phenyl-2-methoxy-2-methoxy-phenyl-2-1-2-1-2-1-2-1.

These photopolymerization initiators may be used alone or in combination of 2 or more. The photopolymerization initiator (D) preferably contains 2 or more kinds of photopolymerization initiators in combination.

In this case, the sensitivity of the photosensitive resin composition can be easily adjusted to an appropriate range.

Among them, an oxime ester compound is particularly preferably used as the photopolymerization initiator (D) from the viewpoint of sensitivity. Oxime ester compounds As examples of preferred compounds, O-acetyl-1- [6- (2-methylbenzoyl) -9-ethyl-9H-carbazol-3-yl ] ethanone oxime, O-acetyl-1- [6- (pyrrol-2-ylcarbonyl) -9-ethyl-9H-carbazol-3-yl ] ethanone oxime, and 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl ] -1-octanone can be cited.

In the case of using an oxime ester compound as the photopolymerization initiator (D), as described above, it is also preferable to use the oxime ester compound in combination with another photopolymerization initiator other than the oxime ester compound.

When an oxime ester compound is used in combination with another photopolymerization initiator, the sensitivity of the photosensitive resin composition can be easily adjusted to an appropriate range. Therefore, excessive curing by exposure is less likely to occur.

As another photopolymerization initiator used in combination with the oxime ester compound, α -aminoalkylphenone-based photopolymerization initiators are preferable α -aminoalkylphenone-based compounds, and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone are mentioned as preferable examples of the photopolymerization initiator.

Since the photosensitive resin composition for forming a light-shielding spacer contains the light-shielding agent (E), the energy required for sufficiently exhibiting the light-shielding characteristics is limited during exposure, and an oxime ester compound and α -aminoalkylphenone-based compound are contained in combination as the photopolymerization initiator (D).

The photopolymerization initiator is 0.1 to 15% by weight, preferably 0.1 to 10% by weight, based on the total weight of the solid contents of the photosensitive resin composition (i.e., excluding the weight of the solvent). for example, 0.1 to 10% by weight of an oxime compound and 0.1 to 10% by weight of an α -aminoalkylphenone-based compound may be used as the photopolymerization initiator, based on the total weight of the solid contents of the photosensitive resin composition (i.e., excluding the weight of the solvent), but the sum of the weights of the oxime compound and α -aminoalkylphenone-based compound is 0.1 to 10% by weight of the total weight of the solid contents of the photosensitive resin composition.

The photopolymerization initiator (D) is a combination of an oxime compound and an α -aminoalkylphenone compound in the above-mentioned range, and can give a photosensitive resin composition having good curing properties and excellent pattern shape.

(E) Light-shading agent

The photosensitive resin composition of the present invention contains a light-screening agent to impart light-screening properties thereto. The sunscreen agent used in the present invention may be a mixture of one or more inorganic or organic sunscreen agents. It preferably has high color productivity and high heat resistance.

The sunscreen may be at least one sunscreen selected from the group consisting of: black organic sunscreen agents, black inorganic sunscreen agents, and sunscreen agents other than black sunscreen agents. Any black inorganic sunscreen, any black organic sunscreen, and any sunscreen other than black sunscreens known in the art may be used.

Specific examples of the black inorganic sunscreen agent may include carbon black, titanium black, metal oxides (e.g., Cu-Fe-Mn-based oxides), and synthetic iron black, etc. Wherein carbon black is preferred for the desired pattern characteristics and chemical resistance.

Specific examples of black organic sunscreen agents may include aniline black, lactam black, perylene black, and the like. Among them, lactam black is preferable for desired optical density, dielectric properties, and the like.

Specific examples of the opacifier other than the black opacifier may include c.i. pigment yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 and 185; c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 215, 216, 224, 242, 254, 255 and 264; c.i. pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38; c.i. pigment blue 15(15:3, 15:4, 15:6, etc.), 16, 21, 28, 60, 64, and 76; c.i. pigment green 7, 10, 15, 25, 36, 47 and 58; c.i. pigment brown 28, etc. Among them, c.i. pigment blue 15:6 is preferable for preventing light leakage.

The amount of opacifier is 10 to 60% by weight, preferably 15 to 50% by weight, based on the total weight of the solid content of the photosensitive resin composition (i.e., excluding the weight of the solvent). Within this range, the pattern formed after development is excellent without affecting the light-shielding property.

In order to uniformly disperse the above preferable light-shading agent in the photosensitive resin composition, a dispersant may be used

Examples of the dispersant may include any known dispersant for sunscreen agents. Specific examples thereof include cationic surfactants, anionic surfactants, nonionic surfactants, zwitterionic surfactants, silicon surfactants, fluorosurfactants, polyester compounds, polycarboxylate compounds, unsaturated polyamide compounds, polycarboxylic acid alkyl salt compounds, polyacrylic acid compounds, polyethyleneimine compounds, polyurethane compounds, polyurethanes, unsaturated polyamides, polycarboxylic acids, amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphates, polyurethane compounds, and the like. These compounds may be used alone or in combination of two or more. Polyacrylic acid compounds and polyurethane compounds are preferably used.

In the production of the photosensitive resin composition, the light-shading agent and the dispersant are mixed at an appropriate ratio to prepare a dispersion, and then the dispersion is added to the photosensitive resin composition.

(F) Additive agent

The photosensitive resin composition of the present invention may further comprise various additives. As the additives, for example, a sensitizer, a surfactant, a curing accelerator, a filler, an antioxidant, a silane coupling agent, a defoaming agent, a photo-initiation aid, and the like are exemplified to improve coatability and prevent generation of defects.

The amount of the additive is not limited herein. The amount of the additive may be 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total solid content (i.e., the content excluding the solvent) of the photosensitive resin composition. Within the above range, the additive does not affect the photosensitivity, development property, curability, etc. of the photosensitive resin composition.

(G) Solvent(s)

The photosensitive resin composition of the present invention is a liquid composition, and the above components and a solvent may be mixed. Any organic solvent known in the art that is compatible with, but not reactive with, the components of the photosensitive resin composition can be used to prepare the photosensitive resin composition.

Examples of the solvent may include glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates, such as cellosolve ethyl acetate; esters, such as ethyl 2-hydroxypropionate; diethylene glycols, such as diethylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate; and alkoxyalkyl acetates, such as 3-methoxybutyl acetate. The solvent may be used alone or in combination of two or more.

The solvent serves to improve coatability of the photosensitive resin composition and to adjust viscosity of the photosensitive resin composition, so the amount of the solvent used is not limited. It is preferably 50 to 90% by weight based on the total weight of the photosensitive resin composition.

The photosensitive resin composition of the present invention as described above can form a cured product having excellent light-shielding properties and excellent adhesion to a substrate. Therefore, it can be suitably used for preparing a light shielding spacer of a liquid crystal display panel.

Method for preparing photosensitive resin composition

The photosensitive resin composition is obtained by respectively mixing the above components at a certain ratio, uniformly dispersing with a stirrer, and filtering with a filter

The present invention also provides a light-shielding spacer made of the photosensitive resin composition.

The photosensitive resin composition of the present invention is used in the same applications as those of known light-shielding spacers and photosensitive resin compositions for black matrices. The following description will specifically explain the case of using the photosensitive resin composition of the present invention as a light-shielding spacer in the method of forming a light-shielding spacer

Generally, a photosensitive composition solution is supplied onto a substrate to be provided with a light-shielding spacer in a film shape or a pattern shape by a method such as coating, and the solvent is dried. Next, a pattern is formed by a method such as photolithography for performing exposure and development. Then, additional exposure or thermal curing treatment is performed as necessary, thereby forming light-shielding spacers on the substrate.

1. Method for coating substrate

The photosensitive resin composition of the present invention is usually applied to a substrate in a liquid state. The coating method can be carried out by a conventionally known method, for example, spin coating, wire bar method, flow coating, dispensing coating, roll coating, spray coating, or the like. Further, the coating may be applied in a pattern by an ink jet method, a printing method, or the like. Among them, the dispensing method is preferable. The dispensing coating method can reduce the amount of the coating liquid used, and is not affected by mist and the like adhering during the use of the spin coating method, and can suppress the generation of impurities and the like,

the amount of coating varies depending on the application, and the dry film thickness of the light-shielding spacer is usually in the range of 0.5 to 10 μm, preferably 1 to 7 μm. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the unevenness is large, a spot defect may occur on the liquid crystal panel. However, when the light-shielding spacer is formed at one time by the photolithography method using the photosensitive resin composition of the present invention, the light-shielding spacer formed finally has a different height.

2. Drying method

Drying after coating the photosensitive resin composition solution on the substrate preferably uses a drying method of hot plate, IR oven, convection oven, vacuum drying.

The drying condition is preferably 60-130 ℃ for 1-3 min.

3. Exposure method

The exposure is performed by superimposing a negative mask pattern on a coating film of the photosensitive resin composition and irradiating a light source of ultraviolet rays or visible rays through the mask pattern.

As a preferable method of the present invention, an exposure mask having a light shielding portion (light transmittance of 0%) and an opening (intermediate transmission opening) having an average light transmittance, which is the plurality of openings, smaller than an opening (full transmission opening) having the highest average light transmittance is used. In this method, a difference in residual film ratio is caused by a difference in average light transmittance (usually 5% to 40%) between the intermediate transmission opening and the full transmission opening, that is, a difference in exposure amount.

For example, a method of forming a middle transmission opening portion by using a matrix-like light-shielding pattern having fine polygonal light-shielding cells is known. Further, a method of controlling light transmittance by using a film of a material such as chromium, molybdenum, tungsten, or silicon as an absorber is known.

The light source used for the above exposure is not particularly limited. Examples of the light source include: a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc lamp, or a fluorescent lamp, or a laser light source such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium-cadmium laser, a blue-violet semiconductor laser, or a near-infrared semiconductor laser. When the optical filter is used by irradiating light of a specific wavelength, the optical filter may be used.

The optical filter may be of a type capable of controlling light transmittance at an exposure wavelength with a thin film, and examples of materials in this case include: cr compounds (Cr oxides, nitrides, oxynitrides, fluorides, etc.), MoSi, Si, W, Al, etc.

The exposure amount is preferably 10mJ/cm2 to 150mJ/cm 2.

In the case of the proximity exposure method, the distance between the exposure object and the mask pattern is preferably 75 μm to 300 μm.

4. Developing method

After the above exposure, a pattern is formed on the substrate by development using an alkaline compound solution.

As the basic compound, there may be mentioned: inorganic basic compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide, and organic basic compounds such as monoethanolamine, diethanolamine, triethanolamine, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide, and choline. The alkaline compound solution may be prepared using one or two or more of the above.

The method of the development treatment is not particularly limited, and the development treatment is usually carried out by a method such as immersion development, spray development, brush development, or ultrasonic development at a development temperature of 10 to 50 ℃, preferably 15 to 45 ℃.

5. Additional exposure and thermal curing treatment

If necessary, additional exposure may be performed on the substrate after development by the same method as the above-described exposure method, or a thermosetting treatment may be performed. The heat curing conditions in this case are preferably a temperature in the range of 150 to 250 ℃ and a time in the range of 10 to 60 min.

The optical filter having the light-shielding spacer of the present invention and the liquid crystal driving side substrate may be bonded to form a liquid crystal cell. Liquid crystal is injected into the formed liquid crystal cell to manufacture a liquid crystal display device.