JP2004066155A - Method of washing tools and materials to which curable composition adheres - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a washing method of removing a curable composition such as a color resist composition or an overcoat composition adhering to tools and materials in a short time with a little labor. <P>SOLUTION: The washing method is carried out using a washing solution containing an aminoalcohol and a polar organic solvent. A curable composition adhering to tools and materials is swollen with the washing solution and then removed. An example of the aminoalcohol is monoethanolamine. The polar organic solvent may be dimethyl sulfoxide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, diethylene glycol monoalkyl ether, γ-butyrolactone, or 3-methyl-3-methoxyethanol. The content ratio of the aminoalcohol and the polar organic solvent is (9 : 1) to (3 : 7) by weight ratio. The content of an inorganic alkaline component is 1% or less. Swelling is carried out at a temperature not lower than 40°C and not higher than 90°C. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for cleaning a device to which a curable composition has adhered, and more specifically, to wash a device used for application, storage, and transportation of the curable composition, and to cure the curable composition attached to the device. It relates to the method of removing.
[0002]
[Prior art]
UV curable compositions that are cured by irradiation with ultraviolet light, and curable compositions such as thermosetting compositions that are cured by heating are useful, such as color resist compositions and overcoat compositions. Is used as a raw material for producing a color filter.
[0003]
Here, the color resist composition is a resist composition that contains a coloring agent such as a pigment and is colored, and is an ultraviolet curable composition that cures when irradiated with ultraviolet light. The overcoat composition is a colorless and transparent composition, and is a UV-curable composition or a thermosetting composition that cures when heated.
[0004]
The color filter is an optical element incorporated in a liquid crystal display device or the like to display an image in color, for example, a transparent color filter layer colored on three primary colors of red, green and blue formed on a substrate. A black and opaque light-shielding layer formed between the colored filter layers, and a colorless and transparent overcoat layer covering these colored filter layers and the light-shielding layer.
[0005]
The colored filter layer and the light-shielding layer constituting such a color filter are formed through a step of applying a color resist composition on a substrate. The color resist composition is usually applied in a state diluted with a polar organic solvent. For example, after applying a black color resist composition on a substrate, the solvent is volatilized to form a coating, and the coating is exposed to ultraviolet light, cured in a predetermined pattern, and then developed. The hardened portion remains as it is and becomes a light shielding layer. On the substrate on which the light-shielding layer is formed, a color resist composition colored in each of the three primary colors is applied, formed into a film, exposed to ultraviolet light, and developed repeatedly for each color, so that the color used is repeated. A colored filter layer colored in the color of the resist composition can be sequentially formed.
[0006]
The overcoat layer is formed through a step of applying the overcoat composition on the substrate on which the colored filter layer and the light shielding layer are formed. The overcoat composition is applied in a state diluted with a polar organic solvent. A solvent is volatilized from the overcoat composition after application to form a coating, and an overcoat layer is formed by irradiating the entire surface of the coating with ultraviolet rays or heating the coating.
[0007]
Such a curable composition may adhere to equipment used when applied on a substrate. In addition, it may adhere to used equipment during storage and transportation. The solvent of the curable composition attached to the equipment evaporates to form a film. The curable composition that has become a film is slightly cured by ultraviolet light contained in ambient illumination light, or is slightly cured with the passage of time even at room temperature, and is firmly attached to equipment.
[0008]
As a method of removing such a curable composition and cleaning the equipment, there is a method of removing the attached curable composition after swelling with warm water. The curable composition is softened by swelling with warm water, and can be removed from the equipment by a method of rubbing off with a cleaning tool such as a spatula. The equipment after cleaning is used again for applying the curable composition.
[0009]
However, such a conventional cleaning method has a problem that a great deal of labor and time are required to scrape off the curable composition.
[0010]
[Problems to be solved by the invention]
Therefore, the present inventors have intensively studied to develop a method for cleaning equipment that can remove the curable composition attached to the equipment in a short time with little effort, and as a result, such a curable composition is obtained from amino alcohol and polar organic solvent. It has been found that when swelled with a cleaning solution, the material can be easily peeled off from the equipment, and can be removed in a short time with a small amount of labor.
[0011]
[Means for Solving the Problems]
That is, the present invention provides a method for cleaning equipment to which the curable composition has adhered, comprising removing the curable composition adhered to the equipment after swelling with a cleaning liquid comprising an amino alcohol and a polar organic solvent. Is what you do.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
Examples of the equipment to be cleaned by the cleaning method of the present invention include parts constituting an application device for applying the curable composition to a substrate, containers used for storing and transporting the curable composition, and the like.
[0013]
An example of the coating device is a spin coater as shown in FIG. Such a spin coater is made of equipment such as a substrate tray (3), a turntable (4), a top plate (5), a current plate (6), a middle plate (7), an inner cup (8), and an outer cup (9). It is configured. These devices are usually made of metal, and aluminum devices are preferably used because they are lightweight, easy to handle, and easy to manufacture. The surface of the aluminum material may be anodized.
[0014]
Examples of the ultraviolet-curable composition that is cured by being irradiated with ultraviolet light include a color resist composition. The color resist composition is a photosensitive composition (resist composition) colored by a coloring agent, and is, for example, a curable composition containing a pigment, an alkali-soluble binder polymer, a photopolymerizable monomer, and a photopolymerization initiator. It is. The color resist composition is colored by a pigment. From a transparent color resist composition which is colored in three primary colors of light (red, green, blue) or three complementary colors (magenta, yellow, cyan), a colored filter layer of a corresponding color is formed. From the color resist composition colored black, a light-shielding layer can be formed. The binder polymer disperses the pigment, and for example, a carboxyl group-containing copolymer which is a copolymer of a carboxyl group-containing monomer and a monomer copolymerizable with the monomer is used. Such a copolymer is soluble in an alkaline aqueous solution as it is. The photopolymerizable monomer is a compound that is polymerized in a chain by light or a photopolymerization initiator to cure the color resist composition. The photopolymerization initiator is a compound that generates a radical or a cation when irradiated with ultraviolet light, and the photopolymerizable monomer starts polymerization by a radical or a cation generated from the photopolymerization initiator. Such a color resist composition is soluble in an alkaline aqueous solution as it is because the binder polymer contained therein is alkali-soluble, but radicals or cations are generated from the photopolymerization initiator by irradiation with ultraviolet rays. The photopolymerizable monomer is cured by polymerization and becomes insoluble in an alkaline aqueous solution. Such a color resist composition is usually applied onto a substrate in a state diluted with a polar organic solvent.
[0015]
In addition, as the UV-curable composition, an UV-curable overcoat composition may also be used. The overcoat composition has the same composition as the color resist composition except that it does not contain a pigment, and is specifically a curable composition containing a binder polymer, a photopolymerizable monomer, and a photopolymerization initiator.
[0016]
Examples of the thermosetting composition which is cured by being heated include a thermosetting overcoat composition. Such an overcoat composition is, for example, a colorless and transparent composition containing a binder polymer and a crosslinking agent. Examples of the binder polymer include an acrylic resin which is a polymer mainly containing acrylic acid units. Examples of the crosslinking agent include polycarboxylic anhydrides. When heated, the coating film of the overcoat composition crosslinks and cures the crosslinking agent, forming a colorless and transparent overcoat layer. Such an overcoat composition is usually applied in a state diluted with a polar organic solvent on a substrate on which a colored filter layer and a light-shielding layer have been formed in advance.
[0017]
In order to apply the curable composition (10) on the substrate (2) using the spin coater (1) shown in FIG. 1, first, the substrate (2) is held on a turntable (4), and The curable composition (10) in a diluted state is dropped on the substrate (2). Next, as shown in FIG. 2, the top plate (5) is lowered to surround the substrate (2) with the rectifying plate (6), the middle plate (7) and the inner cup (8). Surround with outer cup (9). Since the substrate (2) is held by the turntable (4), rotating the turntable also rotates the substrate. When the substrate (2) rotates, the curable composition (10) diluted with the solvent uniformly spreads the surface of the substrate by centrifugal force. Excess curable composition wraps around to the lower side of the substrate and falls or scatters outside, and the substrate tray (3), the turntable (4), the top plate (5), the rectifying plate (6), It adheres to equipment such as the middle plate (7), the inner cup (8) and the outer cup (9). The curable composition adhering to the equipment evaporates from the solvent and dries to form a film. Such a coating is slightly cured by ultraviolet light slightly contained in illumination light, or is slightly cured with time even at room temperature.
[0018]
In the cleaning method of the present invention, such equipment is cleaned to remove the curable composition that has become a film. In order to clean the equipment by the cleaning method of the present invention, first, the attached curable composition is swollen with a cleaning liquid. The cleaning solution comprises an amino alcohol and a polar organic solvent.
[0019]
Examples of the amino alcohol include monoethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 2-amino-1-butanol, 4-amino-1-butanol, and the like. Amines and the like.
[0020]
Examples of the polar organic solvent include dimethyl sulfoxide; N, N-dimethylformamide; N-methyl-2-pyrrolidone; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether; γ-butyrolactone; 3-methyl-3-methoxyethanol; Cellosolve; N, N-dimethylacetamide; hexaalkylphosphoramide such as hexamethylphosphoramide, hexaethylphosphoramide; propylene carbonate; and the like, preferably dimethylsulfoxide, N, N-dimethylformamide, N-methyl -2-pyrrolidone, diethylene glycol monoalkyl ether, γ-butyrolactone, 3-methyl-3-methoxyethanol and the like.
[0021]
The content ratio between the amino alcohol and the polar organic solvent in the cleaning solution is usually about 9: 1 to 3: 7, preferably about 8: 2 to 4: 6, by mass.
[0022]
The cleaning liquid may include water. In addition, the pre-purified water may contain an inorganic alkali component, but if the content of the inorganic alkali component exceeds 1% by mass fraction when the equipment is made of aluminum, the surface of the equipment becomes inorganic alkali component. Since it may be eroded, the content is preferably 1% or less in terms of mass fraction, and more preferably contains substantially no inorganic alkali component. Here, the inorganic alkali component is a basic inorganic compound that generates hydroxide ions by reacting with water, and examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
[0023]
To swell the adhered curable composition with the cleaning liquid, for example, the curable composition may be brought into contact with the same amount or more of the cleaning liquid, and usually, a large amount of the cleaning liquid is used, and the curable composition is adhered. What is necessary is just to immerse the equipment in the cleaning liquid. The curable composition may be swelled at a temperature higher than 90 ° C., but it is practical to swell at 90 ° C. or lower because the amount of evaporating components from the cleaning liquid increases. Although swelling may be performed at a temperature of less than 40 ° C., swelling is preferably performed at a temperature of 40 ° C. or more, since the curable composition can be swelled in a relatively short time. In order to cause swelling in the above temperature range, the device may be immersed in a cleaning solution in the above temperature range. The time required for swelling the curable composition with the cleaning liquid is usually about 0.5 to 4 hours.
[0024]
In order to remove the curable composition after being swollen in this manner from the equipment, it may be rubbed off using, for example, a cleaning tool. Examples of the cleaning tool include a nonwoven fabric, a brush, and a spatula made of a synthetic resin such as nylon, polypropylene, and acrylic. The swollen curable composition is typically scraped off with water. The curable composition swollen with the cleaning liquid specified in the present invention can be removed by scraping off the equipment with a small amount of labor and in a short time.
[0025]
【The invention's effect】
According to the cleaning method of the present invention, a curable composition such as a color resist composition or an overcoat composition adhered to equipment can be removed in a short time with a small amount of labor.
[0026]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.
The substrate tray washed in the following examples is made of aluminum and has a disk shape of 1300 mm in diameter, and a color resist composition (ultraviolet curable composition) or a thermosetting overcoat composition is used in a color filter manufacturing process. This is a part of a spin coater used for coating on a glass substrate. The color resist composition or the overcoat composition is dried and adhered as a film over almost the entire surface.
[0027]
(Example 1)
The substrate tray on which the color resist composition was adhered was immersed in a cleaning solution obtained by mixing monoethanolamine and dimethyl sulfoxide at a mass ratio of 7: 3 at 60 ° C. for 0.5 hour, so that the color resist composition adhered to the substrate tray was obtained. The material was swollen. After immersion, the substrate tray was pulled up from the cleaning solution, and the color resist composition was rubbed off from the surface of the substrate tray using a nonwoven fabric made of nylon while flowing water at room temperature to wash. The film of the color resist composition was easily peeled off, and the time required for the rubbing operation was about 10 minutes. Then, it was further rinsed with water at room temperature, heated at 60 ° C. for 1 hour and dried. There was no coating of the color resist composition on the substrate tray after cleaning, and no fine foreign matter was observed. In addition, the surface of the substrate tray exhibited the same metallic luster as before the color resist composition was attached.
[0028]
(Example 2)
A color resist composition was prepared in the same manner as in Example 1, except that a cleaning solution obtained by mixing monoethanolamine and diethylene glycol monomethyl ether at a mass ratio of 5: 5 was used instead of the cleaning solution used in Example 1. The substrate tray to which the substance was attached was washed. The film of the color resist composition was easily peeled off, and the time required for the rubbing operation was about 10 minutes. There was no coating of the color resist composition on the substrate tray after cleaning, and no fine foreign matter was observed. In addition, the surface of the substrate tray exhibited the same metallic luster as before the color resist composition was attached.
[0029]
(Example 3)
The same operation as in Example 1 was performed, except that the cleaning liquid obtained by mixing monoethanolamine, diethylene glycol monomethyl ether and dimethyl sulfoxide at a mass ratio of 4: 3: 3 was used instead of the cleaning liquid used in Example 1. Then, the substrate tray to which the color resist composition was attached was washed. The film of the color resist composition was easily peeled off, and the time required for the rubbing operation was about 10 minutes. There was no coating of the color resist composition on the substrate tray after cleaning, and no fine foreign matter was observed. In addition, the surface of the substrate tray exhibited the same metallic luster as before the color resist composition was attached.
[0030]
(Example 4)
A substrate tray to which an overcoat composition [a mixture of an acrylic resin and trimellitic anhydride (polycarboxylic anhydride)] was adhered to a cleaning solution obtained by mixing monoethanolamine and dimethyl sulfoxide at a mass ratio of 7: 3. It was immersed at 70 ° C. for 1 hour to swell the adhered overcoat composition. After immersion, the substrate tray was pulled up from the cleaning liquid, and the overcoat composition was rubbed off from the surface of the substrate tray using a nonwoven fabric made of nylon while flowing water at room temperature to wash the substrate tray. The film of the overcoat composition was easily peeled off, and the time required for the scraping operation was about 10 minutes. Further, it was rinsed with water at room temperature, heated at 60 ° C. for 1 hour and dried. There was no overcoat composition on the substrate tray after the cleaning, and no fine foreign matter was observed. The surface of the substrate tray exhibited the same metallic luster as before the overcoat composition was attached.
[0031]
(Example 5)
The same operation as in Example 4 was performed, except that the cleaning liquid obtained by mixing monoethanolamine and N-methyl-2-pyrrolidone at a mass ratio of 6: 4 was used instead of the cleaning liquid used in Example 4, The substrate tray to which the overcoat composition was attached was washed. The film of the overcoat composition was easily peeled off, and the time required for the scraping operation was about 10 minutes. There was no overcoat composition on the substrate tray after the cleaning, and no fine foreign matter was observed. The surface of the substrate tray exhibited the same metallic luster as before the overcoat composition was attached.
[0032]
(Example 6)
The same operation as in Example 4 was performed except that a washing solution obtained by mixing monoethanolamine, diethylene glycol monomethyl ether, water and sodium hydroxide at a mass ratio of 4: 3: 1.5: 1.5 was used as the washing solution. Then, the substrate tray to which the overcoat composition was adhered was washed. The film of the overcoat composition was easily peeled off, and the time required for the scraping operation was about 10 minutes. The substrate tray after the cleaning had no coating of the overcoat composition, and no fine foreign matter was observed. The surface of the substrate tray lost its metallic luster and turned white.
[0033]
(Comparative Example 1)
The substrate tray to which the color resist composition was adhered was washed in the same manner as in Example 1 except that monoethanolamine was used alone instead of the washing solution used in Example 1. The rubbing operation took one hour, but a slight coating of the color resist composition remained on the substrate tray after cleaning.
[0034]
(Comparative Example 2)
The substrate tray to which the color resist composition was attached was washed in the same manner as in Example 1 except that N-methyl-2-pyrrolidone was used alone instead of the washing solution used in Example 1. . Although the rubbing operation took one hour, a relatively large amount of the coating film of the color resist composition remained on the substrate tray after the cleaning.
[0035]
(Comparative Example 3)
The substrate tray to which the overcoat composition was adhered was washed in the same manner as in Example 4 except that monoethanolamine was used alone instead of the cleaning solution used in Example 4. The rubbing operation took one hour, but a relatively large amount of the coating of the overcoat composition remained on the substrate tray after the cleaning.
[0036]
(Comparative Example 4)
The same operation as in Example 4 was carried out except that N-methyl-2-pyrrolidone was used alone instead of the cleaning liquid used in Example 4, as the cleaning liquid, to wash the substrate tray to which the overcoat composition had adhered. . The rubbing operation took one hour, but a relatively large amount of the coating of the overcoat composition remained on the substrate tray after the cleaning.
[0037]
(Comparative Example 5)
Substrate tray to which the color resist composition adhered was operated in the same manner as in Example 1 except that hot water (tap water) was used instead of the cleaning liquid used in Example 1 and immersion was performed at 80 ° C. for 1 hour. Was washed, but most of the color resist composition remained adhered. In place of nylon nonwoven fabric, a spatula made of stainless steel was used to remove the nonwoven fabric over 1 hour while flowing water at room temperature. However, a relatively large amount of the coating film of the color resist composition remained on the washed substrate tray. Was.
[0038]
(Comparative Example 6)
Substrate tray to which the overcoat composition was adhered was operated in the same manner as in Example 4 except that hot water (tap water) was used as the cleaning liquid instead of the cleaning liquid used in Example 4 and immersion was performed at 80 ° C. for 1 hour. Was washed, but most of the overcoat composition remained attached. The stainless steel spatula was used in place of the nylon non-woven fabric, and rubbed off for one hour while flowing water at room temperature. However, a relatively large amount of the coating of the overcoat composition remained on the washed substrate tray. .
[Brief description of the drawings]
FIG. 1 is a diagram schematically illustrating an example of a spin coater that applies a curable composition, and is a diagram illustrating a state in which the curable composition is dropped on a substrate placed on a substrate tray.
FIG. 2 is a view schematically showing a step of applying a curable composition to a substrate by the spin coater shown in FIG. 1, and is a view showing a state where the substrate is rotated.
[Explanation of symbols]
1: coating apparatus 2: transparent substrate 3: substrate tray 4: rotating table 5: top plate 6: rectifying plate 7: middle plate 8: inner cup 9: outer cup 10: curable composition (color resist composition or overcoat) Composition)

Claims (11)

A method for cleaning a device to which a curable composition has adhered, comprising removing the curable composition adhered to the device after swelling with a cleaning liquid comprising an amino alcohol and a polar organic solvent. The washing method according to claim 1, wherein the amino alcohol is monoethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 2-amino-1-butanol or 4-amino-1-butanol. The polar organic solvent is dimethyl sulfoxide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, diethylene glycol monoalkyl ether, γ-butyrolactone, 3-methyl-3-methoxyethanol, butycellosolve, N, N-dimethylacetamide The washing method according to claim 1, wherein the washing method is hexaalkylphosphoramide or propylene carbonate. The cleaning method according to claim 1, wherein the content ratio between the amino alcohol and the polar organic solvent in the cleaning liquid is 9: 1 to 3: 7 by mass. The cleaning method according to claim 1, wherein the equipment is an aluminum equipment, and the content of the inorganic alkali component in the cleaning liquid is 1% or less by mass fraction. The cleaning method according to claim 1, wherein the swelling is performed at a temperature of 40C to 90C. A cleaning liquid comprising an amino alcohol and a polar organic solvent, which is used for cleaning equipment to which a curable composition has adhered. The cleaning solution according to claim 7, wherein the amino alcohol is monoethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 2-amino-1-butanol or 4-amino-1-butanol. The polar organic solvent is dimethyl sulfoxide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, diethylene glycol monoalkyl ether, γ-butyrolactone, 3-methyl-3-methoxyethanol, butyrocellosolve, N, N-dimethyl The cleaning solution according to claim 7, which is acetamide, hexaalkylphosphoramide or propylene carbonate. The cleaning solution according to claim 7, wherein the content ratio between the amino alcohol and the polar organic solvent is 9: 1 to 3: 7 by mass. The cleaning solution according to claim 7, wherein the content of the inorganic alkali component is 1% or less by mass fraction.

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