TW201020696A - Photoresist removing composition - Google Patents

Abstract

The present invention relates to a photoresist removing composition and application, comprising: (a)a water; (b)a quaternary ammonium hydroxide salts; (c)an alkanolamine compound; and (d)a removing composition of nonionic surfactant as shown by structure formula (I): wherein n, and m are defined the same as the specification. The photoresist removing composition of the present invention is suitable used for non-curing photoresists, and especially suitable used for removing non-curing photosensitive composition of color filters.

Description

201020696 IX. Description of the Invention: [Technical Field] The present invention relates to a cleaning solution for a photoresist, which can be applied to a process requiring spin coating, for attaching to a peripheral portion, an edge portion or an inner portion of a substrate. Removal of the uncured photosensitive composition coating film, or cleaning solution for removing the uncured radiation sensitive composition attached to the surface of the device member or device, such as a color filter (CF), a liquid crystal display (LCD) ) or in the field of printed circuit boards (PCBs). It is especially suitable for use in cleaning liquids where the color filter is not cured and the photosensitive composition is removed. [Prior Art] Generally, in a process such as a liquid crystal, an organic EL, or a plasma display, or a semiconductor or a printed circuit board, in order to obtain a fine image, a general composition of 15 lithography techniques is used to form a photosensitive composition. A radiation-sensitive composition such as a photoresist is formed into a film on a substrate by coating. After the radiation, an alkaline cleaning solution is used to remove the unnecessary coating film portion to obtain a good pattern. As a pattern forming method of an RGB*20 resin black matrix manufactured using a color filter for liquid crystal or organic EL, a pigment dispersion method, a dyeing method, a printing method, an electrodeposition method, or the like can be used for the pigment-containing method. The photosensitive composition is subjected to various color mapping methods by photolithography, and a stable color resist film can be obtained, which is suitable for the manufacture of color filters. When the photosensitive composition photoresist film is formed on the substrate by this method, 5 201020696 includes a step of applying a photosensitive composition containing a pigment onto a substrate, and as the coating method, spin coating and slit are known. Coating, cable coating, roller coating, droplet coating, spray coating or a combination of these methods. Further, as a photosensitive composition coating step 5 in the production of a color filter, a photosensitive composition coated by a slit coating method or a coating using a cable is used in addition to the above-described spin coating, or by coating with a cable. Coating by roll coating. However, in this method, it is necessary to remove the unnecessary photosensitive material adhering to a part or all of the coating device after coating the photosensitive composition on each slit nozzle or cable. In addition, it is necessary to carry out the removal of the photosensitive composition of the member attached to the coating device, such as a device pipe for transporting the photosensitive composition. In general, when such a photosensitive composition is removed, a washing liquid is used to carry out washing treatment related equipment and piping. In the past, as a photosensitive composition removing agent, an organic solvent 15 or a mixture thereof is generally used. For example, referring to US Pat. No. 4,983,490, the use of monomethyl ether propylene glycol (PGME) or its ester monodecyl ether propylene glycol ester φ ( Organic solvent such as PGMEA). For example, referring to the patent document of Taiwan TW200615698, photoresist cleaning using an organic solvent component such as monomethyl ether propylene glycol (PGME) or monomethyl ether propylene glycol derivative and cyclohexanone (CYCLOHEXANONE) or cyclohexanone 20 (CYCLOHEXANONE) derivative is used. Agent. However, when it is applied to the removal of the above-mentioned color resist, the photoresist removal property is not sufficiently exhibited, and it is necessary to use a large amount of the removal liquid to cause a waste liquid treatment problem of the organic solvent removal liquid. 6 201020696 Light only has a limited solvent removal effect and there is a dye back-staining condition, which causes environmental pollution and requires equipment to suppress solvent evaporation. In addition, isopropyl alcohol, n-butanol, methyl isobutyl methyl steel and propyl ketone are flammable solvents with low flash point (<38 °C), so there is a risk of fire, and explosion protection is required. The device prevents the occurrence of danger, so the expenditure of the equipment must be raised. Since the general photoresist is an alkali-soluble resin, for example, phenol resin (Novolac), acrylic resin, poly-p-hydroxystyrene, and the like. Therefore, an alkaline substance such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, tetraammonium hydroxide or alkane alcohol is widely used in the cleaning solution of the photoresist. The main components of the 10 strong alkali aqueous solution are sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate. However, due to the possibility of contamination of components due to nano- and unloading of metal ions, liquid crystal panels and semiconductor processes have been gradually replaced with diluted organic alkali solutions, such as tetramethylammonium hydroxide (TMAH) solution or tetraethylammonium hydroxide. (TEAH) and so on. 15 Therefore, the object of the present invention is to provide a cleaning liquid which has good cleaning effect, less residue, low toxicity and less environmental pollution, and does not use a solvent to change the water to dissolve the waste liquid of the organic solvent removal liquid. Handle problems and reduce environmental impact. Moreover, the selection of an excellent surfactant addition can improve the above problems and increase the photoresist removal and removal rate. 20 SUMMARY OF THE INVENTION The present invention discloses a cleaning liquid composition comprising: (4) water; (b) a hydroxy quaternary ammonium salt compound: (4) an alcohol amine compound; and (4) a nonionic compound of the following formula (I) Sexual surfactant: 7 201020696 5

10

2〇

Wherein 'η is an integer from 0 to 10, and ^ is an integer from 4 to 20. In the cleaning liquid composition of the present invention, the ratio of each component is not much limited; generally, it is preferably contained in the composition of the cleaning liquid per 1 part by weight of the component (a). It is 97.9 to 75 parts by weight, the composition 卬) is 1 10 weight damage, the composition damage (C) is 1 to 1 weight part by weight, and the component part (d) is 0·1 to 5 parts by weight. The cleaning liquid composition of the present invention, wherein the compound of the formula (1), preferably, η is 〇 ' m is an integer of 4 to 16. The composition of the cleaning liquid of the present invention has a towel component (8) a oxyhydrogen quaternary salt compound, preferably tetramethylammonium hydroxide. The composition of the cleaning liquid of the present invention is preferably selected from the group consisting of monoethanolamine and a group. The composition of the cleaning liquid of the present invention in which the component (c) the alcohol amine compound diethanolamine and the triethanolamine group can be used for the cleaning of the photoresist containing the coloring agent, in particular, the coloring resist of the resinizable resin The invention is applicable to the adhesive of acrylic resin. The invention also provides a method for cleaning the substrate peripheral photoresist of the color filter, and the substrate peripheral photoresist is combined with the foregoing cleaning liquid composition of the invention. contact. The cleaning liquid composition of the present invention will be described in detail below. In the composition of the cleaning liquid of the present invention, the component (a) water is water which is generally used, and may be, for example, pure water, deionized water or distilled water. Water has the advantages of low toxicity, no ignitability, easy disposal of waste liquid and low cost. The water usage of the present invention may be 99 to 50 Φ parts by weight, preferably 97.9 to 75 parts by weight, based on 100 parts by weight of the total of the cleaning liquid formulation. In the cleaning liquid composition of the present invention, as the component (b) oxyhydrogen quaternary ammonium salt compound, an alkaline aqueous solution prepared from an organic hydrogen oxytetramine salt compound is preferred. Among them, tetramethyl ammonium hydroxide and 2-hydroxyl trimethyl ammonium hydroxide are preferred, and the hydrogen oxytetramine salt of the present invention is 15 The amount of the compound to be used may be 1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total of the cleaning solution. In the cleaning liquid composition of the present invention, specific examples of the component (C) alcohol amine compound are: monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethyl) 2-(2-aminoethoxy ethanol), monoisopropanol amine, diisopropanolamine, triisopropanolamine, n-ethylethanolamine (N- At least one or a mixture of two or more of the compounds such as ethyl ethanolamine and n-butylethanolamine (N-9), and the amount of the alcoholamine compound of the present invention is 100 parts by weight based on the total of the cleaning solution. It may be 〇"~] 〇 by weight, preferably parts by weight. 5 In the cleaning liquid composition of the present invention, regarding the component (d) of the nonionic surfactant of the compound of the formula (I), 11 〇 to an integer of 1〇, the melon is an integer of 4 to 20, preferably, n is 〇, and the melon is an integer of 4 to 16. When the claw ratio is 4 hours, the solubility is insufficient, the photoresist film remains, and the detergency Insufficient The surfactant itself remains on the photoresist film, which reduces the properties of the obtained cleaning film. The nonionic surfactant of the present invention is characterized by the use of a cleaning liquid composition, and is completely formulated with respect to the cleaning solution. When it is 1 part by weight, it may be 0.01 to 10 parts by weight, preferably 01 to 5 parts by weight. When the amount of the component (d) is less than 0.01 part by weight, the effect is insufficient, and when it is more than 1 part by weight, Since the viscosity is increased, the cleaning effect is not good. 15 In the cleaning liquid composition of the present invention, in order to adjust the removal rate, other well-known basic compounds may be used, and examples thereof include the oxidation of an alkali metal such as lithium or potassium sodium. An inorganic compound such as a substance, a hydrogencarbonate, a phosphate, a sulphonate or an ammonia. The cleaning solution of the present invention is an assay solution containing a specific alkali component and a specific nonionic surfactant and water, and the pH thereof. It can be adjusted to ii to be preferable, and more preferably to 12 to 14. When the pH is less than 1 Torr, the residual film is easily generated because the alkalinity is too weak. Further, in the cleaning liquid composition of the present invention, an anionic property can be used. Interface 〖 Surfactants such as other nonionic surfactants, amphoteric surfactant 201020696 agents, and polymeric surfactants. The use of these surfactants can improve the solubility or dispersibility of basic compounds, and can also be adjusted and removed. The cleaning liquid of the present invention is suitably used in a coloring photosensitive resin containing a coloring agent, and the photosensitive resin is not particularly limited, and may be a positive or negative photosensitive resin composition. In the color photosensitive resin composition, it usually contains an organic or inorganic pigment (colorant), an alkali-soluble binder resin, a photosensitive compound, and a solvent. The above β-soluble soluble binder resin may be: a thermoplastic alcohol resin (Novolac 10 resin), a acrylate resin, a maleic anhydride or a half ester thereof. A polymer, a polyhydroxy styrene or the like, wherein an acrylic acid tree is preferred. [Embodiment] 15 The present invention will be described in further detail using the following specific examples. The following examples are given to illustrate the method of the present invention, but the scope of the invention is not limited to the following examples. Parts not specifically marked are based on weight. The cleaning liquid composition of the present invention is used for forming an image by 20 after exposure of a color photoresist. The composition and usage amount of the composition of the color photoresist are as follows: Specific examples of the composition of the components (克) 201020696 Adhesive resin thiol acrylic acid / methyl methacrylate benzyl acetate copolymer 8.40 Polyfunctional monomer Aronix M-400 (for Toagosei Co" Ltd.) 0.24 IRGACURE 907 (for Ciba Specialty Chemicals 0.14 light) Starting agent product) Chemcure-ITX (for Chembridge International Corp) 0.04 Organic solvent Propyleneglycol methyl etheracetate (PGMEA) 9.54 Pigment CI Red Pigment 177 4.00 Formation of color resist film Stir the above ingredients The mixed solution is coated on an alkali-free glass substrate which has formed a 20 μm×20 μm pattern-shaped light-shielding layer, and then coated by spin-rotation to obtain a uniform photoresist film, which is then placed in a vacuum oven at room temperature. 5 minutes solvent extraction, forming a film thickness of 2 / / m thickness of the photoresist film. Removal of color photoresist film "cleaning liquid composition According to the ratio of Table 1, tetramethyl ammonium hydroxide TMAH, monoethanol amine MEA and nonionic surfactant 1 g were added to pure water to prepare 100 g of cleaning solution. Composition. Table 1 12 201020696 Cleaning solution composition pure water (grams) Hydrogen oxytetrazide TMAH (grams) Monoethanolamine MEA (grams) Nonionic surfactant type (1 gram) Color resist residue percentage% Cleaning solution 1 87.7 5 6.3 Nonionic surfactant 1 5 Cleaning solution 2 87.7 5 6.3 Nonionic surfactant 2 55 Cleaning solution 3 87.7 5 6.3 Nonionic surfactant 3 20 Cleaning solution 4 87.7 5 6.3 Nonionic surfactant 4 0 Nonionic surfactant Agent 1 Customized product, the structure is as follows

Non-ionic surfactant 2 Customized product, the structure is as follows 13 201020696

The non-ionic surfactant 3 custom product 'structure is shown below

Η 10 ❹ Non-ionic surfactant 4 Customized product, the structure is as follows

)~~^CH2CH20^-Η Thereafter, the substrate after the photoresist film is applied, the edge is immersed in an aqueous solution of the above-mentioned surface cleaning composition 丨_4 at 23 ° C for 1 , second, and ultrapure After the water was subjected to the cleaning treatment, the percentage of the area of the residual surface of the color resist film was evaluated by visual observation of the portion of the substrate which was washed with the cleaning liquid. 15 201020696 ...丄, not all nonionic surfactants are 清洗 10 first agent cleaning solution. The wrong non-ionic surfactant was used. When it was washed, it was easy to accumulate H and washed (4). According to the nonionic surfactant disclosed in the present invention, pigment microparticles or other water-soluble residue components dissolved in the cleaning are deposited on the substrate or the photoresist film. Thereby, the residue of the cleaning liquid of the present invention can be completely cleaned without causing residue or surface contamination on the color filter. In summary, the present invention exhibits characteristics that are different from conventional techniques in terms of purpose, technique, and efficacy, or in terms of its technical level and R&D design. It is to be noted that the various embodiments described above are for illustrative purposes only, and the scope of the claims is intended to be limited by the scope of the claims. 15 [Simple diagram description] 4%\\ [Main component symbol description] M. 15

Claims (1)

201020696 X. Patent application scope: 1. A cleaning liquid composition comprising: (a) water; (b) a hydroxy quaternary ammonium salt compound; (c) an alcohol amine compound; and (d) (I) Nonionic surfactants for compounds: Wherein η is an integer of 0 to 10, an integer of m*4 to 2〇; wherein, in the cleaning liquid composition per 1 part by weight, the component (a) is 97 9 to 75 parts by weight. The component (b) is 1 to 1 part by weight, the component (4) is 1 to 1 part by weight ', and the component (d) is 0.1 to 5 parts by weight. The cleaning composition according to claim 1, wherein η in the compound of the formula (I) is 〇, and m is an integer of 4 to 16. 3. The cleaning liquid composition according to claim 1, wherein the component (b) the oxyhydrogen quaternary ammonium salt compound is tetramethylammonium hydroxide. 4. The cleaning liquid composition according to claim 1, wherein the component (c) of the alcoholamine compound is one selected from the group consisting of monoethanolamine, diethanolamine, and triethanolamine. 16 201020696 5. The composition of the cleaning liquid according to claim 1, which is suitable for cleaning of a photoresist containing a colorant. 6. The cleaning liquid composition according to claim 1, wherein the cleaning liquid composition is suitable for cleaning with a coloring photoresist using an acrylic resin as a bonding resin. 5 7. A method of cleaning a substrate peripheral photoresist of a color filter, wherein the substrate peripheral photoresist is in contact with a cleaning liquid composition, the cleaning liquid composition comprising: (a) water; ❹ (b a hydroxy quaternary ammonium salt compound; 10 (c) an alcohol amine compound; and (d) a nonionic surfactant of the compound of the following formula (I): 15 wherein the component (a) is contained in an amount of 97.9 to 75 parts by weight per 100 parts by weight of the cleaning liquid composition, and the component (8) is 1 to 10 parts by weight, and the component (c) is 1 to 10 parts by weight. The parts by weight, and the component (d) are 〇丨 5 parts by weight. 8. The cleaning method according to claim 7, wherein n in the compound of the formula (I) is 0, and m is an integer of 4 to 16. The cleaning method according to claim 7, wherein the component (b) the oxyhydrogen quaternary ammonium salt compound is tetrahydroammonium hydroxide. 17 201020696 10. The cleaning method according to claim 7, wherein the component (c) of the alcohol amine compound is selected from the group consisting of monoethyl serotonin, diethanolamine and triethanolamine. one. The cleaning method according to claim 7, wherein the 5 substrate peripheral photoresist is an acrylic resin as a binder resin photoresist. 18 201020696 VII. Designated representative map: (1) The representative representative of the case is: map (none). (2) A brief description of the symbol of the representative figure: (The case is not shown, so there is no component symbol) 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: Among them, the definitions of m and η are as shown in the specification. 4