TW201247865A - Cleaning liquid composition and method of cleaning substrate - Google Patents

Abstract

This invention relate to a cleaning liquid composition and a method of cleaning a substrate and more particularly to a cleaning liquid composition having high biodegradation property and excellent high temperature stability for glass substrates. The cleaning liquid composition comprises: an alkaline compound (A), a compound (B), and the branched surfactant (C) and water (D), wherein the compound (B) is a compound with formula (1) or (2) shown below; in formulae (1) and (2), R1 represents the hydrogen or a C1-6 linear, branched or cyclic alkyl; R2 represents a C1-12 linear, branched or cyclic alkyl; EO represents an ethoxy group; PO represents a propoxy group; the average of (m+n) is 1-30; and the average of (p+q) is 0.5-10. The branched surfactant (C) is represented by formula (3) below: R3-O-(EO)a(PO)b-H, wherein R3 represents a C6-20 branched alkyl, alkenyl, or acyl or C12-20 branched alkyl-substituted phenyl; EO represents an ethoxy group; PO represents a propoxy group; a represents an integer of 1-20; and b represents an integer of 0-20.

Description

201247865 VI. Description of the Invention: [Technical Field] The present invention relates to a cleaning liquid composition and a method for cleaning a substrate, and more particularly to providing a glass substrate having good biodegradability and high temperature stability. A liquid composition, and a method of washing a substrate using the cleaning composition. [Prior Art] In the preparation of a liquid crystal display, whether it is a color filter substrate or a thin film transistor array substrate, it must be cleaned with a cleaning solution before photoresist film formation, so the cleaning technique will Affecting the quality of the subsequent photolithography, in order to achieve a good cleaning effect, the wettability of the cleaning liquid on the substrate can be increased. Generally, the industry often improves by adding a surfactant. The wettability, as disclosed in Japanese Patent Laid-Open No. 2004-094241, discloses the use of an acetyiene dioxime-based surfactant which can suppress the generation of foaming in addition to improving the wettability to the surface of the substrate. Although the above-mentioned conventional cleaning liquid can effectively increase the wettability to the surface of the substrate, there is a problem that the biodegradability is poor and the high temperature stability is poor. In view of this, the inventor of the present case has been devote himself to research, and the invention has been innovated and rich in industrial value. SUMMARY OF THE INVENTION A main object of the present invention is to provide a composition for a cleaning liquid, particularly a cleaning liquid composition which is excellent in biodegradability and high in temperature stability for cleaning a glass substrate. 201247865 In order to meet the intended purpose, the present invention provides a cleaning liquid composition package 3, although compound (1), compound (8), branched interface (4) (〇 and water (D); wherein 'compound (B) has the following structural formula (1) or a compound of the formula (2); R2 〇-(ΕΟ)·^Η 〜 〜〇—(Ε〇)-(ρ〇)--η

Structural formula (1) ο-(ΕΟ) <Γ^Η 〇—_“(ρ〇) η Structural formula (2), 'η configuration (1) and structural formula (2), recalling hydrogen atom a linear, branched or cyclic alkyl group having a carbon number of 1 to 6; R2 represents a linear, branched or cyclic group having a carbon number of 1 to 12; Ε0 represents an ethoxy group; The average value of (m+n) is u; the average value of (p+Q) is 5~ι〇; the branched surfactant (C) is represented by the following structural formula (3); R3-0- (EO)a(p〇)b_H Structural Formula (3) In the structural formula (3), R3 represents a carboxyl group having 6 to 2 Å, a carboxyl group having a bond group, an alkenyl group or a fluorenyl group or a carbon number of 2 to 2 a phenyl group substituted with a branched alkyl group; E 〇 represents an ethoxy group; P0 represents a propoxy group; a represents an integer of 卜; b represents an integer of 0 to 20. The present invention provides a substrate cleaning In the method, the composition of the cleaning liquid as described above is used. The following is a detailed description of each composition of the present invention. [Furrification liquid composition] Basic compound (A) 201247865 The composition of the cleaning liquid of the present invention is used. The basic compound (A) contains an inorganic basic compound (Ai) and/or an organic basic compound (A 2) Specific examples of the inorganic basic compound (A-1) of the present invention include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide; diammonium hydrogen phosphate and disodium hydrogen phosphate; Alkali metal or ammonium phosphates such as dipotassium hydrogen phosphate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, etc.; alkali metal silicates such as lithium niobate, sodium niobate, and niobic acid An alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate; an alkali metal borate such as lithium borate, sodium borate or potassium borate; wherein an alkali metal hydroxide is preferred. (A-I) may be used singly or in combination of plural kinds. The organic basic compound (A-2) of the present invention contains a quaternary ammonium hydroxide-based compound and an organic compound of an organic amine. Specific examples of the quaternary ammonium salt compound are, for example, tetramethyl ammonium hydroxide, tetraethylamine hydroxide, tetrapropylamine hydroxide, tetrabutylammonium hydroxide, 2-hydroxy-triammonium hydroxide (2-hydroxyl trimethyl ammonium hydroxide And other compounds; and specific examples of organic amines are: monodecylamine, diamine, tridecylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylpropamine ), diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol (2-(2-8111丨11061:11€«7)61;11311〇1), monoisopropanolamine , diisopropanolamine, triisopropanolamine, n-ethylethanolamine, n-butylethanolamine, N,N-dimethylethanolamine, N,N-difluorene A compound such as propylamine, N,N-dimethylisopropanolamine (N, N-dimethyl 6 201247865 isopropanolamine), cyclohexylamine, morpholine or the like. The above organic basic compound (A 2 ) may be used singly or in combination of plural kinds. Since the organic compound (A-2) of the present invention does not contain a metal ion in the production, it is less likely to cause a residual effect on a semiconductor element such as a thin film transistor. Among them, monoethanolamine, diethanolamine, triethanolamine, and early isopropanolamine are preferred. Compound (B) The compound (B) used in the composition of the cleaning liquid of the present invention has a compound of the following formula (1) or formula (2); r2

0- Η R2' 〇—(EO)-(P〇)-

-H

.^〇-(ΕΟ)-(Ρ〇)^η Structural Formula (1) Structural Formula (2), '. In the formula (1) and the formula (2), Ri represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and R2 represents a direct bond, a bond or a bond having a carbon number of 1 to 12. a cyclic alkyl group; E0 represents an ethoxy group; p〇 represents a propoxy group; (m+n) has an average value of 1 to 30; (p+q) has an average value of 〇. 5~1〇. As described above, the average value of 〇n+n) is usually from 1 to 3 Å, preferably from 3 to 25 Å, more preferably from 5 to 20. The average value of (p + q) is usually 〇 5 to 1 Torr, preferably 1 to 9, more preferably 2 to 8. The compound (B) used in the composition of the cleaning solution of the present invention can be measured by a 13C nuclear magnetic resonance spectrometer (13C hidden Spectn py) (the average of 201247865 of _ and (p+q). In the compound (B) of the present invention Specific examples of the compound represented by the structural formula (1) are, for example, trade names Surfynol 420, Surfynol 440, Surfynol 450, Surfynol 465, Surfynol 485, Dynol 604, Dy:nol 607 (manufactured by Air Products and Chemicals), etc. In the compound (B), the preparation of the compound represented by the structural formula (2) can be referred to the paragraphs 0069 to 0080 of the US Published Patent No. 2002/0106589 A1, which will not be further described herein. The above compound (B) can be used alone. In the cleaning liquid composition of the present invention, the compound (B) is usually used in an amount of 10 to 5 parts by weight, preferably 30, based on 1 part by weight of the basic compound (A). ～450 parts by weight, more preferably 50 to 4 parts by weight. If the compound (B) is not used at all, the cleaning solution has a problem of poor high temperature stability. Branched surfactant (C) Washing according to the invention Clean liquid composition, including the following structure The bond type surfactant (C) represented by the formula (3). R3-0-(E0)a(P0)bH Structural formula (3) In the structural formula (3), Ra represents a carbon number of 6 to 2 a branched alkyl group, an alkenyl group or a fluorenyl group or a phenyl group substituted with a branched alkyl group having a carbon number of 12 to 20; E0 represents an ethoxy group; P0 represents a propoxy group; and a represents 丨~2〇 Integer; b represents an integer of 〇~20; in the case of b, when b represents an integer from 1 to 20, the arrangement of E0 and P0 may be block or random. In the formula (3), when b=〇, (E〇XP〇)b consists of only ethoxy groups. When b is represented as an integer of u, it means that (10)a(10)b is composed of B.201247865 oxy group and propoxy group. When Na is composed of ethoxy group and propoxy group The arrangement of E0 and P0 may be a block or a random one. When the arrangement of 〇 and P0 is a loose segment, as long as each average is within the above range, the number of blocks of E0 and P〇 The number of segments may be i or two or more. When the number of blocks of EG is 2, the number of repetitions of each towel may be the same or different; the number of blocks of P0 is two or more. The number of repeats in each block may be the same or different. When the arrangement of 0 and P0 is block or random, if the molar ratio [Meo/Mpo] with p〇 is 9. 5/0. 5~5/5, high water solubility can be achieved. And (10)) a(p 〇)b, based on high water solubility, a is preferably 丨 15 , more preferably 〜 10, b is preferably 1 -15, more preferably 1 〜 1 G, (a + b) is preferred. It is 2 to 3 inches, more preferably 2 to 20. The branched surfactant represented by the structural formula (3) is described above (for example, the product name is SINOPOL E8002, SINOPOL E8003, SIN0P0L E8008, SINOPOLE8015C, and the Japanese synthetic chemical system), Lutens〇1 τ〇3,

Lutensol® 05, Lutensol® 07, Lutensol TO10 (manufactured by BASF), Newcol 1004, Newcol 1006, Newcol 1008, Newcol 1020 (manufactured by Japan Emulsifier), NONION EH-204, NONION EH-208 (manufactured by Nippon Oil Co., Ltd.), and the like. The above-mentioned branched surfactants (C) may be used singly or in combination of plural kinds. In the cleaning liquid composition of the present invention, the branched surfactant is used in an amount of 1 part by weight based on the basic compound (A) (the amount used is usually 1 to 50 parts by weight, preferably 30 to 450 parts by weight). The part by weight is more preferably 50 to 400 parts by weight. If the branched surfactant (C) is not used at all, the composition of the cleaning solution may have a problem that the decomposition property of 201247865 is low. Water (D) The present invention The water (D) used in the composition of the cleaning liquid is not particularly limited. It has distilled water, pure water (water obtained by desalting treatment such as Linzijia Naxi), and ultrapure water (except inorganic ions). It does not contain organic matter, bacteria, microparticles, and solvent, and the neighboring waters of the county. The water (D) used in the present invention is based on the adverse effect of metal ions on the electronic control circuit. Preferably, the pure water or the ultrapure water is more preferably ultrapure water. The ultrapure water can be sterilized by ultraviolet light irradiation or the like by passing the tap water through activated carbon, ion exchange treatment, steam treatment, or if necessary. Over-receiving device: According to the resistance value of 25: (:: the resistance value is above 1 Μ Ω · cm or more In the case of pure water, the electric resistance value is Ω·cm or more, which is called ultrapure water. The cleaning liquid composition of the present invention is based on the basic compound (A) and the weight of the water (D) is usually 5〇〇~3〇, 〇〇〇 by weight, preferably 5〇〇~20, 000 parts by weight, more preferably 5〇〇~15, 〇〇〇 by weight. Linear type surfactant (E) In the cleaning liquid composition of the present invention, a linear surfactant (e) represented by the following structural formula (4) may be further added as needed; R4-0-(E0)c(P0)dH structural formula (4) In the formula (4), 'R4 represents a linear alkyl group, an alkenyl group or a fluorenyl group having a carbon number of 8 to 18, or a linear alkyl group-substituted phenyl group having a carbon number of 14 to 18; Oxyl; PO represents propoxy; c and d are the average addition moles of EO and PO, respectively, c represents an integer from 1 to 20, and d represents an integer of 〇~2〇. (E〇X(P〇) The arrangement of EO and p〇 in d may be block type or random type. 201247865 , '° configuration (4) 'when d=0' means (E0)c(:P0)d only by B The oxy group constitutes 'when d is an integer of i~2〇, it means that (10)c(10)d is derived from ethoxy group and When propionate (10). (10)d is composed of ethoxy group and propoxy group, the arrangement of 'E0 and P〇' may be a block or a random one, wherein when the arrangement of 仞 and P0 is block, as long as When the average number is within the above range, the number of blocks of the shell E E0 and the number of blocks of P 可以 may be two or more, respectively. When the number of blocks of E0 is two or more, each block is used. The number of repetitions may be the same 'may be different; when the number of blocks of PG is two or more, the number of repetitions in each block may be the same or different. When the arrangement of E0 and P0 is block or random, if E The molar ratio of 〇 to p〇 [Meo/Mpo] is 9. 5/0. 5~5/5, which can achieve high water solubility. And in (10)c(P0)d, 'based on the water solubility consideration, C is preferably from 1 to 15, more preferably from 1 to 1, preferably from 1 to 15, more preferably from 1 to 10, and (c+d) is preferred. It is 2 to 30, more preferably 2 to 20. The linear surfactant (e) represented by the above structural formula (4) contains a compound of the following formula (5) to (9):

CjH2j+i-〇-(E〇)rH Structural Formula (5) CjH2j+i-〇-(E〇)s(p〇)tH Structural Formula (6) CjH2j+i-〇-(p〇)s(E 〇) tH Structural formula (7) CjH2j+, -0-(E0)u(P0)v(E0)wH Structural formula (8) CjH2J+i-0-(E0)s(P0)tH Structural formula (9) EO and P〇 of the structural formulae (6) to (8) are block arrangements, E0 and P0 of the structural formula (9) are randomly arranged, j represents an integer of 8 to 18, and r, s, t, u, v, and w represent E0. Or the average addition molar number of P0, r means an integer of 1 to 20's represents an integer of 1~2〇't represents an integer of 1~2〇, u 201247865 represents an integer of 1~10, and v represents HO An integer, w represents an integer. Specific examples of the linear surfactant (E) represented by the structural formula (4) are as follows: octanol, decyl alcohol, decyl alcohol, twelve scales, stearyl stearyl alcohol, oleyl alcohol, octyl An ethoxy group and/or a propoxy group-added compound of a compound such as ruthenium, osmium or ruthenium ruthenium, a trade name of SINOPOL 1308FG (manufactured by Sino-Japanese Synthetic Chemical Co., Ltd.), MMONK-204, _I〇nk-220, ION K-230, _face P-2G8, Guan Bing P-21G, _: drying E-202, _ surface ε-205, _ drawing S-207, _I0N S-220C made in Japan, EMULGEN 103, EMULGEN 220, EMULGEN 350, EMULGEN LS-1G6, EMULGEN LS-11G (made by Kao Chemical). The linear surfactants (E) described above may be used singly or in combination of plural kinds. In the cleaning liquid composition of the present invention, the linear surfactant (8) is usually used in an amount of from 10 to 250 parts by weight based on 1 part by weight of the basic compound (A). More preferably, it is 20 to 200 parts by weight. When the amount of the linear surfactant (E) used is from 1 to 300 parts by weight, the biodegradability of the cleaning liquid composition can be further improved. Additive (F) In the cleaning liquid composition of the present invention, optionally, an additive (F) can be further added, such as an antifoaming agent, a chelating agent, an antioxidant, a pH adjuster, a buffering solvent, a preservative, and a water-soluble solution. Organic solvents, dispersants, etc. The cleaning liquid composition of the present invention may further contain an antifoaming agent as needed, and specific examples thereof include a polyoxane type, a higher alcohol type, a polyether type, a fatty acid type, a polyethylene glycol type, and a mineral oil type. Contains the following formula: (1〇) Table 12 201247865 shows the compound:

In the structural formula (10), X represents an integer of 1 or 2; and R represents a functional group represented by the following structural formula (丨1).

OH

In the structural formula (11), y represents an integer of 3 to 7. Specific examples of the compound represented by the above structural formula (10) include, for example, Surfynoi MD-20 and Surfynol MD-30 (manufactured by Air Products and Chemicals Co., Ltd.). The above antifoaming agents may be used singly or in combination of plural kinds or more. Specific examples of the chelating agent of the present invention are: ethylenediaminetetraacetic acid (salt) (EDTA), diethylenetriaminepentaacetic acid (salt) (DTPA), triethylenetetramine hexaacetic acid (salt XTTHA), hydroxyethylethylene Amine triacetate (HEDTA), dihydroxyethyl ethylenediaminetetraacetic acid (salt) (DHEDDA), nitrilotriacetic acid (salt) (NTA), hydroxyethyliminodiacetic acid (salt) ( HIDA), /3-alanine diacetic acid (salt), aspartic acid diacetic acid (salt), decylglycine diacetate (salt), imidodisuccinic acid (salt), serine Aminopolycarboxylic acid such as acetic acid (salt), hydroxyiminodisuccinic acid (salt), dihydroxyethylglycine (salt), aspartic acid (salt), glutamic acid (salt), etc. Salt); hydroxycarboxylic acid (salt) such as glycolic acid (salt), tartaric acid (salt), citric acid (salt), gluconic acid (salt), etc.; mercapto diphosphonic acid (salt), amine tris(arylene) Phosphonic acid) (salt), 1-hydroxyethylidene-1,1-diphosphine 13 201247865 acid (salt), ethylenediaminetetrakis (methylene phosphonic acid) (salt), hexamethylenediamine tetra(methylene) Phosphonic acid) (salt), propylenediamine tetra ( Mercaptophosphonic acid (salt), diethylenetriamine penta (methylene phosphonic acid) (salt), triethylenetetramine hexa(methylene phosphonic acid) (salt), triamine triethylamine hexa Methylene phosphonic acid) (salt), trans-1,2-cyclohexanediamine tetra (methylene phosphonic acid) (salt), glycol ether diamine tetra (methylene phosphonic acid) (salt), four a phosphonic acid (salt) such as ethylene pentaamine (methylene phosphonic acid) (salt); condensed phosphoric acid (salt) such as metaphosphoric acid (salt), trimeric squaric acid (salt), hexametaphosphoric acid (salt), etc. . The above-mentioned chelating agents may be used singly or in combination of plural kinds or more. Specific examples of the antioxidant of the present invention are: 2,6-di-t-butylbenzene, 2-tert-butyl-4-decyloxybenzoquinone, 2,4-dimethyl-6-tributyl Phenols such as phenol; monooctyldiphenylamine, monodecyldiphenylamine, 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, tetrabutyldiphenylamine, tetrahexyl An amine of the limb, α-cacine, phenyl-α-ceamine, etc.; phenothiazine, pentaerythritol tetrakis(3-laurylthiopropionate), bis (3, 5-third) a sulfur system such as bis(3,5-t-butyl-4-hydroxybenzyl)sulfide; di(2,4-di-tert-butylphenyl) a phosphorus system such as pentaerythritol ester, monophenylisobutyl phosphite, diphenyl diisooctyl phosphite, or triphenyl phosphite. The above-mentioned antioxidants may be used singly or in combination of plural kinds or more. Specific examples of the pH adjuster of the present invention include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, sulfamic acid, and phosphoric acid; inorganic bases such as hydrogen peroxide, sodium hydroxide, and potassium hydroxide. The above-mentioned pH adjusters may be used singly or in combination of plural kinds or more. Specific examples of the buffering solvent of the present invention include: formic acid, acetic acid, calcined acid, lactic acid, malic acid, acid, butyl butyric acid, pyruvic acid, malonic acid, organic acid and salt such as 201247865. ; two, inorganic acids and their salts. The above-mentioned buffering solvent may be used alone or in combination of plural kinds or more. For example, a preservative of the present invention, for example, hexahydro 4,3,5-tris(indenyl)-s-salt or the like 4 (triazine). a derivative; 12 benzoisomorpholin-3-one, 2-methyl-4-isothiazolin-3-one, 5-nitrox-2-methyl-4_rithiazin-3-one, etc. Isothiaz〇lin derivative; 4_(2: nitro-T-)H-ethyl '2-nitrotrimethylene) morphine derivative such as dimorphine; 2-(4-thiazole a benzimidazole derivative such as benzimidazole or the like. The above-mentioned preservatives may be used singly or in combination of plural kinds or more. The water-soluble organic solvent of the present invention preferably has a solubility in water of 2 (g/100 g) or more in the case of 2 (rc), more preferably 10 or more. It has a coffee such as dimethyl hydrazine, butadiene wind, 3亚 环 甲基 飒 2 2 2 2 甲基 甲基 甲基 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; - amines such as methylformamide, N-methylamine, N,N-dimethylacetamide, N,N-dimethylpropionamide; N-methyl-2-pair Fine, N-ethyl-2-pyrene ketone H methyl-2-. 醢 略 等 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; , lactones such as pentane vinegar; ethylene glycol, ethylene glycol monomethyl ketone, ethylene glycol monoethyl amide, diethylene glycol, diethylene glycol monodecyl amide, methanol, ethanol, isopropanol, etc. Ether-ethyl alcohol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, propylene glycol, propanol monomethyl Ether, dipropylene glycol monodecyl hydrazine, 1,3-butanediol, diethylene, alcohol dimercapto ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether Monoethyl alcohol, a glycol diethyl ether, etc., and glycol ethers Yue-yl methyl 2 _2_ evil 15201247865 Oh spit saliva anger burning of steel drink Si

Hydrogen oxime and the like. The above water-soluble organic solvent may be a single ketone ketone, 3, 5-dimethyl-2-(oxazolidinone) acrylonitrile, benzonitrile or the like, propyl carbonate, etc., ketone, cyclohexanone, ring; Or use a mixture of more than one. The more the classification of the present invention, ethyl _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ ), sea salt, cationized starch and other polysaccharides and derivatives thereof; phytic acid (phy^c acid), bis(polyoxyethylene) alkyl ether phosphate, tris(polyoxyethylene) alkyl shhed acid, etc. Polyphenol (poval) and its phosphates. The above dispersing agents may be used singly or in combination of plural kinds or more. In the additive (F) used in the present invention, the antifoaming agent is used in an amount of from 0.1 to 1 part by weight, preferably from 3 to 9 parts by weight, based on 1 part by weight of the basic compound (A). More preferably, it is 5 to 8 parts by weight; the amount of the chelating agent is usually 30 parts by weight or less, preferably 1 to 2 parts by weight, more preferably 3 to 2 parts by weight; antioxidant, buffer solvent, antiseptic The amount of the agent and the dispersing agent to be used is usually 10 parts by weight or less, preferably 8 parts by weight or less, more preferably 5 parts by weight or less, and the pH adjusting agent is usually used in an amount of 90 parts by weight or less, preferably 85 parts by weight or less or less. More preferably, it is 80 parts by weight or less; the amount of the water-soluble organic solvent used is usually 500 parts by weight or less, preferably 400 parts by weight or less, more preferably 300 parts by weight or less. [Method for Cleaning Substrate] 201247865 The present invention further provides a method for cleaning a substrate which is cleaned by using a pre-prefective (4) cleaning hybrid; the specific cleaning means include, but are not limited to, soaking Method, shower method, brushing method, ultrasonic cleaning method and bubble; end washing method. Wherein, the immersion method is filled in the immersion tank with the composition of the cleaning liquid, and then the substrate is immersed in the composition of the cleaning liquid; the rinsing method is to clean the substrate with the composition of the cleaning liquid, such as Cailin, Confucianism and Confucianism; In the method, the substrate is cleaned by a tool such as a sponge or a brush. The composition of the cleaning liquid of the present invention can be applied to the cleaning of a glass substrate such as soda lime glass, borosilicate glass, cerium oxide glass or alkali-free glass. The cleaning composition of the present invention is at 25. The cloud point of the time is 4〇~55. (〕, preferably 42 to 52 ° C, more preferably 45 to 5 (TC. When the composition of the cleaning liquid at 25 C, the cloud point is 40 to 55 ° C, the brittleness of the substrate [Evaluation method] (1) Take the 25 C (room temperature) washing solution composition 5 〇mi into a transparent glass beaker, and place the beaker on a hot plate to heat, heat and magnetize at the same time. When the composition of the cleansing liquid is completely converted into a white turbidity, the temperature of the composition of the washing liquid is measured as a cloud point. (2) Biodegradability The composition of the washing liquid is The water was diluted to 1%, and then the chemical oxygen demand (9) D) was measured using DRB200 (manufactured by HACH), and the biodegradability was evaluated according to the following criteria: ◎ : COD < 2000 ppm 17 201247865 Ο · 2000 ppm ^ COD < 3000 ppm Δ · 3000ppm^COD<4000ppm X*4000ppm^COD (3) High temperature stability The dilution composition was diluted to 5% with water, and then the diluent was heated to 70 C for 240 hours, followed by visual observation of the diluent. Whether or not sediment is produced, and the biodegradability is evaluated according to the following criteria: 〇: no precipitate is produced X: there is a sink The present invention will be further illustrated by the following examples, but it should be understood that the examples are merely illustrative. It is intended to be illustrative, and should not be construed as limiting the practice of the invention. [Preparation of Compound (B)] <Preparation Example 1> Add Surfyn〇ii〇4 (Air) to a 1000 ml still steel.

The E0 adduct (manufactured by Products and Chemicals) (I 〇 content is i. 3 mol) 341 g (1.2 mol) and was purged with nitrogen to vent air. Then, the pressure cooker was pressurized to 6.7 bar, and after heating to the fairy, the syringe was added with three syringes to add diethyl ether (b〇r〇n meter (1) 赃池 diethyletherate M·2g. Then, using a syringe pump to respectively 1.5mL The flow of /min and l.OmL/min was simultaneously added with ethylene oxide 175g (3.97 mol) and propylene oxide (piOpylene 〇xide) 600g (10.3 mol), and after the addition, Addition of three defeated silver II 201247865 diethyl ether 0. 7g, and stirred at 45 ° C for 6 hours, after cooling to obtain the compound (B-3X expressed by Surfynol 104 / EOPO). The obtained compound (β-3) with nuclear magnetic Resonance spectrometer measured (m + n) was 5.1, (p + q) was 9.7. <Preparation Example 2> Surfynol 44〇Wir was added to a 1000 ml autoclave

Product and Chemicals) 400g (1.05 m), and after introducing a nitrogen gas after sealing, the air is discharged. Next, trimethylamine 2·37 g (0.04 mol) was added using a gas-tight syringe, and the autoclave was pressurized to 6.7 bar and heated to 1 〇〇C. Then, 120 g of propylene oxide (2.06 mol) was added at a flow rate of l.〇mL/min using an injection pump, and the mixture was stirred at 1 ° C for 12 hours after the addition. Finally, the product was removed by cooling, and heated under vacuum for 13 hours to remove the compound (B-4) (expressed as Surfynol 440/PO). The obtained compound (B-4) was measured by a nuclear magnetic resonance spectrometer to have (111 + 11) of 3 8, (p + q) of 1. 9. [Examples and Comparative Examples] <Example 1> 100 parts by weight of a hydroxide hydroxide (hereinafter referred to as A-1-1) and 200 parts by weight of Surfynol 465 (manufactured by Air Products and Chemicals, hereinafter referred to as Bl) And 160 parts by weight of a branched surfactant (Lutensol T07, manufactured by BASF, hereinafter abbreviated as c_1;) and 25 parts by weight of water (D)' are uniformly mixed by a rocking stirrer to obtain the present invention. The composition of the cleaning solution was evaluated by the evaluation methods in the past, and the results are shown in Table 1. <Examples 2 to 9 > The same operation method as in Example 1 was carried out except that the type of the raw material of 201247865 and the amount thereof were changed, and the formulation and evaluation results are shown in Table 1. <Comparative Examples 1 to 4> The operation method similar to that of Example 1 was different in that the type of the raw material and the amount thereof were changed, and the formulation and evaluation results are shown in Table 。. It can be seen from the above examples and comparative examples that the cleaning liquid composition of the present invention has good biodegradability and high temperature stability; Comparative Example 丨3 does not simultaneously use compound (β) and branched surfactant (C). Therefore, there is a problem that the biodegradability is poor or the temperature stability is not good; in the comparative example 4, the conventional substrate treatment solution is used, and good biodegradability and high temperature stability are still not obtained, and Example 4 and Example 6 The biodegradability of Examples 4 and 6 was better than the other examples due to the further use of the linear surfactant (Ε). In addition, the cloud point of each of the implements of the present invention is between 40 and 55 Å, and the cleaning power of the glass substrate is good. However, the above description is only a preferred embodiment of the present invention. When it is not possible to limit the forest (4), it is a simple test of the scope of the invention and the content of the invention. It is still within the scope of the invention patent. [Description of the Schedule] ^Composition and Evaluation of Examples and Comparative Examples of the Composition of the Cleaning Liquid of the Invention 20 201247865 Table 1 Composition Examples Comparative Example 1 2 3 4 5 6 7 8 9 1 2 3 4 Basic Compound ( A) (parts by weight) Α-1-1 100 100 100 100 90 70 100 100 100 Α-1-2 100 100 80 Α-2-1 10 Α-2-2 30 20 Compound (B) (parts by weight) Β -1 200 100 15 200 6 Β-2 200 100 150 50 Β-3 160 500 200 Β-4 100 Branched surfactant (C) (parts by weight) C-1 160 160 100 60 160 C-2 140 140 60 50 500 C-3 15 Water (D) (parts by weight) D 2500 2500 2500 2000 800 800 5000 2000 4500 2500 2500 2500 10000 Linear surfactant (E) (parts by weight) Ε-1 100 150 Ε-2 120 Additives (F) ί Rays) F-1 15 6 F-2 8 2 Evaluation item Cloud point 49 50 48 45 46 43 48 50 48 53 54 50 . Biodegradability 〇〇〇 ◎ 〇 ◎ 〇〇〇〇 XXX high temperature stability〇〇〇〇〇 〇〇〇〇X 〇XX "-" means that cloud point 无法-1-1 Α-1-2 Α-2-1 Α-2-2 potassium hydroxide sodium hydroxide monoethanolamine tetramethylamine hydrazine cannot be measured -1 Surfynol 465 Structural Formula (1) (m+n)=10 Air product and Chemicals Β-2 Surfynol 485 Structural Formula (1) (m+n)=30 Air product and Chemicals Β-3 Surfynol 104/EOPO Structural Formula (2)(m+n)=5.1 ; 〇>fq)=9.7 Β-4 Surfynol 440 fPO Structural Formula (2) (m+n)=3.8 ; (p+q)=1.9 C-1 Lutensol T07 BASF System C -2 SINOPOL E8015 Sino-Japanese Synthetic 彳b-C-3 Newcol 1006 曰 Emulsifier Ε-1 SINOPOL 1308FG 曰 曰 曰 F-2 F-1 F-2 Emalgen LS-106 Phosphate r-valerolactone Kao Chemical System 3 21

Claims (1)

201247865 VII. Patent application scope: 1. A cleaning liquid composition comprising: a basic compound (A); a compound (B); a branched surfactant (C); and water (D); wherein: a compound Compound (B) has the following structural formula (丨) or structural formula (2 r:, Ο-(EO) -H m r2 Ο—(EO)~(p〇)一"Η Ο—(EO) Ο—(ΕΟ)-(Ρ0)^η Structural Formula (1) Structural Formula (2) In Structural Formula (1) and Structural Formula (2), 吣 represents a hydrogen atom, and the carbon number i -6 is linear or branched. a cyclic alkyl group; R2 represents a linear, branched or cyclic alkyl group having a carbon number of 丨~i2; E0 represents an ethoxy group; P0 represents a propoxy group; and an average value of (m+n) is 1~ 30; (p+q) has an average value of 0 5 to 10; branched surfactant (c) is represented by the following structural formula (3); R3-〇-(EO)a(P〇)bH structural formula ( 3) In the formula (3), R3 represents an alkyl group, an alkenyl group or a fluorenyl group having a bond number of 6 to 2 Å, or a phenyl group having a branched chain alkyl group having a carbon number of 12 to 20; Indicates an ethoxy group; K) represents a propoxy group; a represents an integer of 1 to 20; and b represents an integer of 〇-20. The liquid cleaning composition according to the first aspect of the invention, wherein the compound (B) is used in an amount of ^ 5 parts by weight based on the basic compound (« 100 parts by weight) The type of surfactant (c) is used in an amount of from 1 〇 to 500 parts by weight, and the amount of water (D) used is from 500 to 30,000 parts by weight. 3. The composition of the cleaning solution as described in claim 1 Further, it further contains a direct bond type surfactant (e) represented by the following structural formula (4); R4-0-(E0)c(P0)dH structural formula (4) In the structural formula (4), R4 represents a linear alkyl group having a carbon number of 8 to 18 or a linear or alkyl group substituted with a linear alkyl group having a carbon number of 14 to 18; E 〇 represents an ethoxy group; PO represents a propoxy group; An integer of 1 to 2 ;; d is an integer of 〇 20. 4. The cleaning composition according to claim 3, wherein the basic compound (A) is based on 100 parts by weight, a linear type The amount of the surfactant (E) is from 1 to 300 parts by weight. 5. The composition of the cleaning solution according to claim 1, wherein the composition is at 25. (The cloud point is between 40) ~55 ° C. 6. One A cleaning method for a substrate, which uses the cleaning liquid composition according to any one of claims 1 to 5. 23 201247865 IV. Designation of representative drawings: (1) The representative representative of the case is: ( ) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: