TWI434927B - Washing liquid composition and substrate cleaning method - Google Patents

Description

Cleaning liquid composition and substrate cleaning method

The present invention relates to a cleaning liquid composition and a method for cleaning a substrate, and more particularly to providing a cleaning liquid composition having good biodegradability and high temperature stability against a glass substrate, and a cleaning composition using the same The method of cleaning the substrate.

In the preparation of the liquid crystal display, whether it is a color filter substrate or a thin film transistor array substrate, the photoresist must be cleaned before the photoresist is formed, so the cleaning technology will affect the subsequent The quality of photolithography, in order to achieve a good cleaning effect, can increase the wettability of the cleaning liquid on the substrate. Generally, the industry often uses the addition of a surfactant to improve the wettability, such as The use of an acetylene diol-based surfactant is disclosed in Japanese Patent Laid-Open Publication No. 2004-094241, which can suppress the wettability of the surface of the substrate and suppress the occurrence of foaming.

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 this case is the focus of research on the bet, and the invention is innovated and rich in industrial value.

SUMMARY OF THE INVENTION A primary 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.

To satisfy the intended purpose, the present invention provides a cleaning liquid composition comprising a basic compound (A), a compound (B), a branched surfactant (C), and water (D); wherein the compound (B) is a compound having the following structural formula (1) or structural formula (2);

In the structural formula (1) and the structural formula (2), R ₁ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and R ₂ represents a linear chain having 1 to 12 carbon atoms. a branched or cyclic alkyl group; EO represents an ethoxy group; PO represents a propoxy group; (m+n) has an average value of from 1 to 30; (p+q) has an average value of from 0.5 to 10; The type of surfactant (C) is represented by the following structural formula (3);

R ₃ -O-(EO) _a (PO) _b -H Structural formula (3)

In the formula (3), R ₃ represents a branched alkyl group, an alkenyl group or a fluorenyl group having 6 to 20 carbon atoms, or a phenyl group substituted with a branched alkyl group having 12 to 20 carbon atoms; EO represents an ethoxy group. A group; PO represents a propoxy group; a represents an integer of 1 to 20; and b represents an integer of 0 to 20.

The present invention provides a method of cleaning a substrate using the cleaning composition as described above.

The components of the present invention are described in detail below.

[washing liquid composition] Basic compound (A)

The basic compound (A) used in the cleaning liquid composition of the present invention contains an inorganic basic compound (A-1) 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, etc.; 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; alkali metal silicates such as lithium niobate, sodium citrate, potassium citrate An alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate; or an alkali metal borate such as lithium borate, sodium borate or potassium borate. Among them, an alkali metal hydroxide is preferred. The above inorganic basic compound (A-1) 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 basic organic compound. Specific examples of the above quaternary ammonium hydroxide-based compound are, for example, tetramethyl ammonium hydroxide, tetraethylamine hydroxide, tetrapropylamine hydroxide, tetrabutylamine hydroxide, 2-hydroxy-hydroxide A compound such as 2-hydroxyl trimethyl ammonium hydroxide; and specific examples of organic amines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine , diisopropylamine, monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, monoisopropanolamine, two Isopropanolamine, triisopropanolamine, n-ethylethanolamine, n-butylethanolamine, N,N-dimethylethanolamine, N,N-dimethyl A compound such as propanolamine, N,N-dimethyl 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 basic compound (A-2) of the present invention does not contain metal ions in production, it is less likely to cause adverse effects such as residual images on semiconductor elements such as thin film transistors. Among them, monoethanolamine, diethanolamine, triethanolamine, and monoisopropanolamine 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 structural formula (1) or structural formula (2);

In the structural formula (1) and the structural formula (2), R ₁ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and R ₂ represents a linear chain having 1 to 12 carbon atoms. A branched or cyclic alkyl group; EO represents an ethoxy group; PO represents a propoxy group; (m+n) has an average value of 1 to 30; and (p+q) has an average value of 0.5 to 10.

As described above, the average value of (m + n) is usually from 1 to 30, preferably from 3 to 25, more preferably from 5 to 20. The average value of (p+q) is usually from 0.5 to 10, preferably from 1 to 9, more preferably from 2 to 8.

The used cleaning solution composition of the present invention, the compound (B) using ¹³ C nuclear magnetic resonance spectroscopy ⁽¹³ C NMR Spectroscopy) measurement of (m + n) and (p + q) of the average value.

In the compound (B) of the present invention, specific examples of the compound represented by the formula (1) are, for example, trade names Surfynol 420, Surfynol 440, Surfynol 450, Surfynol 465, Surfynol 485, Dynol 604, Dynol 607 (Air Products and Chemicals). System) and so on.

In the compound (B) of the present invention, 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 is not described herein.

The above compound (B) may be used singly or in combination of plural kinds.

In the cleaning liquid composition of the present invention, the compound (B) is used in an amount of usually 10 to 500 parts by weight, preferably 30 to 450 parts by weight, more preferably 50%, based on 100 parts by weight of the basic compound (A). 400 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)

The cleaning liquid composition of the present invention comprises the branched surfactant (C) represented by the following structural formula (3).

R ₃ -O-(EO) _a (PO) _b -H Structural formula (3)

In the formula (3), R ₃ represents a branched alkyl group, an alkenyl group or a fluorenyl group having 6 to 20 carbon atoms, or a phenyl group substituted with a branched alkyl group having 12 to 20 carbon atoms; EO represents an ethoxy group. PO; represents a propoxy group; a represents an integer from 1 to 20; b represents an integer from 0 to 20; (EO) _a (PO) _b , when b represents an integer from 1 to 20, the arrangement of EO and PO Can be block or random.

In the structural formula (3), when b=0, it means that (EO) _a (PO) _b is composed only of an ethoxy group, and when b is an integer of 1 to 10, it means (EO) _a (PO) _b system. It consists of ethoxy and propoxy. When (EO) _a (PO) _{b is} composed of an ethoxy group and a propoxy group, the arrangement of EO and PO may be a block or a random one, wherein when the arrangement of EO and PO is a block, as long as each When the average value is within the above range, the number of blocks of EO and the number of blocks of PO may be one or two or more. When the number of blocks of EO is two or more, the number of repetitions in each block may be the same or different, and when the number of blocks of PO is two or more, the number of repetitions in each block may be the same or different.

When the arrangement of EO and PO is block or random, if the molar ratio of EO to PO [M _EO /M _PO ] is 9.5/0.5 to 5/5, high water solubility can be achieved. In (EO) _a (PO) _b , a is preferably from 1 to 15, more preferably from 1 to 10, more preferably from 1 to 15, more preferably from 1 to 10, based on high water solubility. a+b) is preferably 2 to 30, more preferably 2 to 20.

The specific examples of the branched surfactant (C) represented by the structural formula (3) are as follows: trade names SINOPOL E8002, SINOPOL E8003, SINOPOL E8008, SINOPOL E8015 (manufactured by Sino-Japanese Synthetic Chemical Co., Ltd.), Lutensol TO3, Lutensol TO5, Lutensol TO7, Lutensol TO10 (manufactured by BASF), Newcol 1004, Newcol 1006, Newcol 1008, Newcol 1020 (manufactured by Nippon Emulsifier), NONION EH-204, NONION EH-208 (manufactured by Nippon Oil Co., Ltd.), and the like.

The above-mentioned branched type surfactant (C) may be used singly or in combination of plural kinds.

In the cleaning liquid composition of the present invention, the amount of the branched surfactant (C) is usually 10 to 500 parts by weight, preferably 30 to 450 parts by weight, based on 100 parts by weight of the basic compound (A). More preferably 50 to 400 parts by weight. If When the branched surfactant (C) is not used at all, the detergent composition has a problem that the biodegradability is low.

Water (D)

The water (D) used in the cleaning liquid composition of the present invention is not particularly limited. Specific examples thereof include distilled water, pure water (water obtained by deionization treatment by ion exchange resin, etc.), ultrapure water (excluding inorganic ions, containing no organic matter, bacteria, fine particles, and dissolved gas) and have been proposed in recent years. Various functional waters, etc. The water (D) used in the present invention is preferably pure water or ultrapure water, more preferably ultrapure water, based on the metal ion having a poor influence on the electronic control circuit. The ultrapure water may be obtained by passing the tap water through activated carbon, ion exchange treatment, distillation treatment, irradiation with ultraviolet light if necessary, or passing through a filter. According to the resistance value of 25 °C, the resistance value is 1MΩ. Above cm, it can be called pure water, and the resistance value is 10MΩ. More than cm can be called ultrapure water.

The cleaning liquid composition of the present invention is usually used in an amount of 500 to 30,000 parts by weight, preferably 500 to 20,000 parts by weight, more preferably 500 to 15,000, based on 100 parts by weight of the basic compound (A). Parts by weight.

Linear 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; R ₄ -O-(EO) _c (PO) _d -H structural formula (4)

In the formula (4), R ₄ 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; EO represents an ethoxy group. 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 from 0 to 20. The arrangement of EO and PO in (EO) _c (PO) _d may be a block type or a random type.

In the structural formula (4), when d=0, it means that (EO) _c (PO) _d is composed only of ethoxy groups, and when d is an integer of 1 to 20, it means (EO) _c (PO) _d system. It consists of ethoxy and propoxy. When (EO) _c (PO) _{d is} composed of an ethoxy group and a propoxy group, the arrangement of EO and PO may be a block or a random one, wherein when the arrangement of EO and PO is a block, as long as each When the average value is within the above range, the number of blocks of EO and the number of blocks of PO may be one or two or more. When the number of blocks of EO is two or more, the number of repetitions in each block may be the same or different, and when the number of blocks of PO is two or more, the number of repetitions in each block may be the same or different.

When the arrangement of EO and PO is block or random, if the molar ratio of EO to PO [M _EO /M _PO ] is 9.5/0.5 to 5/5, high water solubility can be achieved. In (EO) _c (PO) _d , based on the high water solubility consideration, c is preferably from 1 to 15, more preferably from 1 to 10, and d is preferably from 1 to 15, more preferably from 1 to 10, (c+ d) is preferably 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 structural formula (5) to (9): C _j H _2j+1 -O-(EO) _r -H structural formula ( 5)

C _j H _2j+1 -O-(EO) _s (PO) _t -H Structural formula (6)

C _j H _2j+1 -O-(PO) _s (EO) _t -H Structural formula (7)

C _j H _2j+1 -O-(EO) _u (PO) _v (EO) _w -H Structural formula (8)

C _j H _2j+1 -O-(EO) _s (PO) _t -H Structural formula (9)

Wherein, the EO and PO of the structural formulas (6) to (8) are arranged in blocks, the EO and PO of the structural formula (9) are randomly arranged, and j represents an integer of 8 to 18, r, s, t, u, v And w represents the average addition of EO or PO, and r represents 1~ An integer of 20, s represents an integer from 1 to 20, t represents an integer from 1 to 20, u represents an integer from 1 to 10, v represents an integer from 1 to 10, and w represents an integer from 1 to 10.

Specific examples of the linear surfactant (E) represented by the structural formula (4) are, for example, octanol, decyl alcohol, tridecyl alcohol, dodecanol, stearyl alcohol, stearyl alcohol, oleyl alcohol, An ethoxylated and/or propoxylated compound of a compound such as octylphenol, nonylphenol or dodecylphenol, trade name SINOPOL 1308FG (made by Sino-Japanese Synthetic Chemical Co., Ltd.), NONION K-204, NONION K- 220, NONION K-230, NONION P-208, NONION P-210, NONION E-202, NONION E-205, NONION S-207, NONION S-220 (made by Nippon Oil & Fats), EMULGEN 103, EMULGEN 220, EMULGEN 350 , EMULGEN LS-106, EMULGEN LS-110 (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 (E) is used in an amount of usually 1 to 300 parts by weight, preferably 10 to 250 parts by weight, based on 100 parts 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) such as an antifoaming agent, a chelating agent, an antioxidant, a pH adjuster, a buffering solvent, a preservative, a water-soluble organic solvent, and a dispersion may be further added. Agents, etc.

Further, the cleaning liquid composition of the present invention may further contain an antifoaming agent, and specific examples thereof include polyfluorene-based, higher alcohol-based, polyether-based, fatty acid ester-based, polyethylene glycol-based, and mineral oil-based Contains the compound represented by the following structural formula (10):

In the formula (10), x represents an integer of 1 or 2; and R represents a functional group represented by the following structural formula (11).

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) are, for example, trade name Surfynol MD-20, 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) (TTHA), hydroxyethyl Ethylenediaminetriacetic acid (salt) (HEDTA), dihydroxyethylethylenediaminetetraacetic acid (salt) (DHEDDA), nitrilotriacetic acid (salt) (NTA), hydroxyethyliminodiacetic acid (salt) (HIDA), β-alanine diacetic acid (salt), aspartic acid diacetic acid (salt), methyl glycine diacetic acid (salt), imidodisuccinic acid (salt), serine Aminopolycarboxylic acid such as diacetic acid (salt), hydroxyiminodisuccinic acid (salt), dihydroxyethylglycine (salt), aspartic acid (salt), glutamic acid (salt), etc. (salt); hydroxycarboxylic acid (salt) of glycolic acid (salt), tartaric acid (salt), citric acid (salt), gluconic acid (salt), etc.; methyl diphosphonic acid (salt), aminotris(methylenephosphonic acid) (salt), 1-hydroxyethylidene-1,1-diphosphonic acid (salt), ethylenediaminetetrakis (methylenephosphonic acid) (salt) , hexamethylene diamine tetra (methylene phosphonic acid) (salt), propylene diamine tetra (methylene phosphonic acid) (salt), diethylene triamine penta (methylene phosphonic acid) (salt), triethylene tetra Amine hexa (methylene phosphonic acid) (salt), triamine triethylamine hexa(methylene phosphonic acid) (salt), trans-1,2-cyclohexanediamine tetra (methylene phosphonic acid) (salt), a phosphonic acid (salt) such as a glycol ether diamine tetra (methylene phosphonic acid) (salt), tetraethylenepentamine (methylene phosphonic acid) (salt), or the like, a metaphosphoric acid (salt), Condensed phosphoric acid (salt) such as tripolyphosphate (salt) or hexametaphosphoric acid (salt). 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-tert-butylphenol, 2-tert-butyl-4-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol Phenol type; monooctyldiphenylamine, monodecyldiphenylamine, 4,4'-dibutyldiphenylamine, 4,4'-dipentyldiphenylamine, tetrabutyldiphenylamine, tetrahexyldiphenylamine, Amines such as α-naphthylamine and phenyl-α-naphthylamine; phenothiazine, pentaerythritol tetrakis(3-laurylthiopropionate), bis(3,5-tert-butyl-4) a sulfur system such as bis(3,5-t-butyl-4-hydroxybenzylsulfide); bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, Phosphorus such as monophenylisobutyl phosphite, diphenyl diisooctyl phosphite, and 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; and inorganic bases such as lithium hydroxide, 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 buffer solvent of the present invention are: formic acid, acetic acid, succinic acid, Organic acids and salts such as lactic acid, malic acid, butyric acid, maleic acid, pyruvic acid, malonic acid, gallic acid; inorganic acids such as phosphoric acid and boric acid, and salts thereof. The above-mentioned buffering solvents may be used singly or in combination of plural kinds or more.

Specific examples of the preservative of the present invention include triazine derivatives such as hexahydro-1,3,5-tris(hydroxyethyl)-s-triazine; 1,2-benzisothiazoline-3; -isothiazolin derivatives such as ketone, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one; 4-( a morpholine derivative such as 2-nitrobutyl)morpholine or 4,4-(2-ethyl-2-nitrotrimethylene)dimorpholine; 2-(4-thiazolyl)benzimidazole Benzimidazole derivatives and 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 3 (g/100 g) or more at 20 ° C, more preferably 10 or more. Specifically, for example, dimethyl hydrazine, cyclobutyl hydrazine, 3-methylcyclobutyl fluorene, 2,4-dimethylcyclobutyl fluorene, etc.; dimethyl hydrazine, diethyl hydrazine, double (2- Anthraquinones such as hydroxyethyl)hydrazine; N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N,N-dimethylpropanamide Such as guanamine; N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, etc.; β-propiolactone, β-butane Lactones such as esters, γ-butyrolactone, γ-valerolactone, δ-valerolactone, alcohols such as methanol, ethanol, and isopropanol; ethylene glycol, ethylene glycol monomethyl ether, and B Glycol monoethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol Alcohol monophenyl ether, triethylene glycol monomethyl ether, propylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 1,3-butylene glycol, diethylene glycol dimethyl ether, diethylene glycol Alcohol diethyl ether, triethylene glycol dimethyl ether, Ethylene glycol and glycol ethers such as triethylene glycol triethyl ether; oxazoles such as N-methyl-2-oxazolidinone and 3,5-dimethyl-2-oxazolidinone An oxazolidinone; a nitrile of acetonitrile, propionitrile, butyronitrile, acrylonitrile, methacrylonitrile, benzonitrile, etc.; carbonates; carbonates such as ethylene carbonate and propylene carbonate a ketone such as acetone, diethyl ketone, acetophenone, methyl ethyl ketone, cyclohexanone, cyclopentanone or diacetone; a cyclic ether such as tetrahydrofuran or tetrahydropyran. The above-mentioned water-soluble organic solvents may be used singly or in combination of plural kinds or more.

Specific examples of the dispersing agent of the present invention are: hydroxyethyl cellulose, cationized cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, guar gum, cationized guar gum, and trisin ( Polysaccharides and derivatives thereof such as xanthan gum), alginate, cationized starch, etc.; phytic acid, bis(polyoxyethylene) alkyl ether phosphate, tris(polyoxyethylene) alkyl ether phosphate, 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 0.1 to 10 parts by weight, preferably 0.3 to 9 parts by weight, more preferably 0.5%, based on 100 parts by weight of the basic compound (A). 8 parts by weight; the chelating agent is usually used in an amount of 30 parts by weight or less, preferably 1 to 20 parts by weight, more preferably 3 to 20 parts by weight; the antioxidant, buffer solvent, preservative and dispersing agent are usually used in an amount of usually 10 parts by weight or less, preferably 8 parts by weight or less, more preferably 5 parts by weight or less; the pH adjusting agent is usually used in an amount of 90 parts by weight or less, preferably 85 parts by weight or less, more preferably 80 parts by weight or less; The amount of the water-soluble organic solvent to be 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 of cleaning substrate]

The present invention further provides a method for cleaning a substrate, which is to clean the substrate by using the cleaning composition of the present invention; the specific cleaning means include, but are not limited to, a soaking method, a shower method, a brushing method, and an ultrasonic wave. Washing method and foam 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 washes the substrate by washing, spraying, spraying, etc.; In the brushing method, the substrate is cleaned by a tool such as a sponge or a brush.

The cleaning liquid composition 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 liquid composition of the present invention has a cloud point of 40 to 55 ° C at 25 ° C, preferably 42 to 52 ° C, more preferably 45 to 50 ° C. When the cloud composition has a cloud point of 40 to 55 ° C at 25 ° C, the detergency for the glass substrate is good.

[Evaluation method] (1) cloud point

Pour 50ml of the cleaning solution composition at 25 ° C (room temperature state) into a 100 ml transparent glass beaker, and heat the beaker on a hot plate, while heating and stirring the composition of the cleaning solution with a magnetic stirrer, to be washed. When the liquid composition was completely converted into a white turbid shape, the temperature of the composition of the washing liquid was measured as a cloud point.

(2) Biodegradability

The composition of the cleaning solution was diluted with water to 1%, and then the chemical oxygen demand (COD) was measured using DRB200 (manufactured by HACH), and the biodegradability was evaluated in accordance with the following criteria.

◎: COD<2000ppm

○: 2000 ppm ≦ COD < 3000 ppm

△: 3000ppm ≦COD<4000ppm

×: 4000 ppm ≦ COD

(3) High temperature stability

The detergent composition was diluted with water to 5%, and then the diluted solution was heated to 70 ° C for 240 hours, and then the dilution was visually observed for the presence of precipitate, and the biodegradability was evaluated according to the following criteria.

○: no precipitate is produced

×: There is sediment production

The present invention will be further exemplified by the following examples in order to provide a further understanding of the present invention, and the purpose and effect of the present invention, but it should be understood that these embodiments are for illustrative purposes only and should not be It is to be construed as limiting the implementation of the invention.

[Preparation of Compound (B)] <Preparation Example 1>

An EO adduct (EO content: 1.3 mol) of Surfynol 104 (manufactured by Air Products and Chemicals) was added to 341 g (1.2 mol) of a 1000 ml autoclave, and after sealing, nitrogen gas was introduced to discharge the air. The autoclave was then pressurized to 6.7 bar, and after heating to 40 ° C, 1.2 g of boron trifluoride diethyletherate was added using a syringe. Then, using an injection pump, ethylene oxide 175 g (3.97 mol) and propylene oxide (propylene) were simultaneously added at a flow rate of 1.5 mL/min and 1.0 mL/min, respectively. Oxide) 600g (10.3 mol), and after adding 0.7g of boron trifluoride diethyl ether, and stirring at 45 ° C for 6 hours, after cooling to obtain compound (B-3) (to Surfynol 104 / EOPO Express). The obtained compound (B-3) was analyzed by a nuclear magnetic resonance spectrometer to have (m+n) of 5.1 and (p+q) of 9.7.

<Preparation Example 2>

In a 1000 ml autoclave, Surfgol 440 (manufactured by Air Products and Chemicals) 400 g (1.05 mol) was added, and after sealing, nitrogen gas was introduced to discharge the air. Next, 2.37 g (0.04 mol) of trimethylamine was added using a gas-tight syringe, and the autoclave was pressurized to 6.7 bar and heated to 100 °C. Then, 120 g of propylene oxide (2.06 mol) was added using a syringe pump at a flow rate of 1.0 mL/min, and after the addition was completed, the mixture was stirred at 100 ° C for 12 hours. Finally, the product was removed by cooling, and heated under vacuum for 13 hours to remove the trimethylamine to give the compound (B-4) (in the form of Surfynol 440/PO). The obtained compound (B-4) was measured by a nuclear magnetic resonance spectrometer to have (m+n) of 3.8 and (p+q) of 1.9.

[Examples and Comparative Examples] <Example 1>

100 parts by weight of potassium hydroxide (hereinafter referred to as A-1-1), 200 parts by weight of Surfynol 465 (manufactured by Air Products and Chemicals, hereinafter abbreviated as B-1), and 160 parts by weight of branched interfacial activity A detergent (Lutensol TO7, manufactured by BASF, hereinafter referred to as C-1) and 2500 parts by weight of water (D) are uniformly mixed by a shaker to obtain a cleaning liquid composition of the present invention, and the cleaning liquid composition The evaluation methods were previously evaluated, and the results are shown in Table 1.

<Examples 2 to 9>

The operation method similar to that of Example 1 differs in that the kind of the raw material and the amount thereof are 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 differs in that the kind of the raw material and the amount thereof are changed, and the formulation and evaluation results are shown in Table 1.

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 Examples 1 to 3 do not simultaneously use the compound (B) and the branched surfactant (C). Therefore, there is a problem that the biodegradability is poor or the high 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; Examples 4 and 6 are Further use of the linear type surfactant (E) makes the biodegradability of Example 4 and Example 6 superior to the other examples. Further, in each of the examples of the cleaning liquid composition of the present invention, the cloud point is between 40 and 55 ° C, and the cleaning power of the glass substrate is good.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All should remain within the scope of the invention patent.

[Note to the attached table]

Table 1 shows the composition and evaluation results of the examples and comparative examples of the composition of the cleaning solution of the present invention.

Claims (6)

A cleaning liquid composition comprising: a basic compound (A); a compound (B); a branched surfactant (C); and water (D); wherein: the compound (B) has the following structural formula (1) Or a compound of formula (2); In the structural formula (1) and the structural formula (2), R ₁ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; and R ₂ represents a linear chain having 1 to 12 carbon atoms. a branched or cyclic alkyl group; EO represents an ethoxy group; PO represents a propoxy group; (m+n) has an average value of from 1 to 30; (p+q) has an average value of from 0.5 to 10; The type of surfactant (C) is represented by the following structural formula (3); R ₃ -O-(EO) _a (PO) _b -H. In the structural formula (3), R ₃ represents a carbon number of 6 to a branched alkyl group, an alkenyl group or a fluorenyl group, or a phenyl group substituted with a branched alkyl group having 12 to 20 carbon atoms; EO represents an ethoxy group; PO represents a propoxy group; and a represents a group of 1 to 20 An integer; b represents an integer from 0 to 20. The cleaning liquid composition according to the first aspect of the invention, wherein the compound (B) is used in an amount of 10 to 500 parts by weight based on 100 parts by weight of the basic compound (A), and a branched surfactant ( The amount of use of C) is 10 to 500 parts by weight, and the amount of water (D) used is 500 to 30,000 parts by weight. The cleaning liquid composition according to claim 1, further comprising a linear surfactant (E) represented by the following structural formula (4); R ₄ -O-(EO) _c (PO) _d -H In the structural formula (4), R ₄ 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 having a carbon number of 14 to 18 Phenyl; EO represents ethoxy; PO represents propoxy; c represents an integer from 1 to 20; and d represents an integer from 0 to 20. The cleaning liquid composition according to the third aspect of the invention, wherein the linear surfactant (E) is used in an amount of from 1 to 300 parts by weight based on 100 parts by weight of the basic compound (A). The composition of the cleaning solution according to claim 1, wherein the composition has a cloud point of from 40 to 55 ° C at 25 ° C. A method of cleaning a substrate, which comprises using the cleaning liquid composition according to any one of claims 1 to 5.