JP3799026B2 - Alkaline cleaner - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to an alkaline cleaning agent used for removing oils and fats, resins, particles, etc. adhering to electronic parts, metal parts, ceramic parts, etc., more specifically, a vertically-aligned polyimide film (particularly semi-fired) for liquid crystal panels. The present invention relates to an alkaline cleaning agent used as a stripping solution for film formation.
[0002]
[Prior art]
Conventionally, alkaline cleaners have better ability to remove oils, fats, resins, particles, etc. than neutral cleaners, so they are widely used in production sites for electronic parts, metal parts, ceramic parts, etc. . However, since the alkaline cleaning agent easily corrodes non-ferrous metals such as aluminum, it is currently impossible to use it for cleaning electronic parts and the like in which aluminum is used for some or all of the parts.
For example, the polyimide alignment film for electronic components, particularly liquid crystal panels, has been a horizontal alignment type so far, but the demand for a wide viewing angle liquid crystal panel is increasing, and the number of vertical alignment type polyimide alignment films is increasing. If the horizontal alignment type polyimide alignment film glass substrate is in a semi-baked state (semi-cured film desolvated at about 80 ° C.) before complete baking (baking temperature: about 180 ° C.), the defective product is N-methylpyrrolidone, etc. The alignment film can be peeled off without corroding the aluminum thin film (wiring) with the above solvent, but in the case of the vertical alignment type polyimide alignment film, the polyimide alignment film (semi-firing) is not used with the solvent even in the semi-baked state. Since the film cannot be peeled off, the alignment film is peeled off using an alkali cleaning agent. At that time, the aluminum thin film (wiring) on the glass substrate is corroded, so the aluminum thin film portion is protected and washed with wax, and then the wax is removed with a solvent such as hydrocarbon to regenerate the substrate, or at the same time with the alignment film A method has been adopted in which only the glass substrate is regenerated after the aluminum thin film has been completely peeled off and dissolved.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel cleaning agent excellent in aluminum corrosion resistance, a cleaning method, and a cleaned electronic component.
[0004]
[Means for Solving the Problems]
  As a result of intensive studies to achieve the above object, the present inventor has reached the present invention.
  That is, the present invention comprises an organic alkali (A7) represented by the general formula (1) and a 3 to 8 valent aliphatic polyhydric alcohol (B2) having a molecular weight of 92 to 400 that does not contain a nitrogen atom. The weight ratio of A7) to aliphatic polyhydric alcohol (B2) is 1/99 to 50/50For peeling alignment film of liquid crystal panelAlkaline detergents;AndA cleaning method for an aluminum-use member, characterized in that the cleaning agent is cleaned by at least one method selected from ultrasonic cleaning, shower cleaning, spray cleaning, immersion and immersion rocking. It is.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
(A) in the present invention includes (A1) metal hydroxide [alkali metal hydroxide (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkaline earth metal hydroxide (calcium hydroxide, water) Magnesium oxide, barium hydroxide, etc.)], (A2) carbonate [alkali metal salts (sodium carbonate, potassium carbonate, etc.), alkaline earth metal salts (calcium carbonate, magnesium carbonate, barium carbonate, etc.)], (A3) phosphorus Acid salts [alkali metal salts (sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, potassium tripolyphosphate, etc.), alkaline earth metal salts (calcium pyrophosphate, magnesium pyrophosphate, barium pyrophosphate, calcium tripolyphosphate, magnesium tripolyphosphate, tripolylin Barium acid)], A4) Silicate [alkali metal salt (sodium silicate, potassium silicate, etc.), alkaline earth metal salt (calcium silicate, magnesium silicate, barium silicate, etc.)], (A5) ammonia, (A6) hydroxyl Examples include amines, (A7) organic alkalis represented by the following general formula (1), and mixtures thereof.
[0006]
[Chemical Formula 3]
[Formula 4]
[In the formula, R¹Is a hydrocarbon group having 1 to 24 carbon atoms, R², R^ThreeAnd R^FourAre respectively H, a hydrocarbon group having 1 to 24 carbon atoms or a group represented by the general formula (2), and R^FiveRepresents an alkylene group having 2 to 4 carbon atoms, and p represents an integer of 1 to 6. ]
[0007]
In the general formula (1), R¹Examples thereof include linear or branched saturated or unsaturated hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic ring-containing hydrocarbon groups. As the linear or branched saturated hydrocarbon group, an alkyl group (methyl group, ethyl group, n-, i-, sec- and t-butyl group, octyl group, 2-ethylhexyl group, octadecyl group, etc.); Examples of the linear or branched unsaturated hydrocarbon group include an alkenyl group (vinyl group, propenyl group, allyl group, butenyl group, etc.); examples of the alicyclic hydrocarbon group include a cycloalkyl group (such as a cyclohexyl group); Examples of the ring-containing hydrocarbon group include aryl groups (phenyl group, naphthyl group, etc.); aralkyl groups (benzyl group, phenethyl group, etc.); alkylaryl groups (methylphenyl group, ethylphenyl group, nonylphenyl group, methylnaphthyl group, And ethyl naphthyl group). Of these hydrocarbon groups, alkyl and alkenyl groups are preferred from the viewpoint of detergency.
[0008]
R¹The carbon number of is usually 1-24, preferably 1-14. R¹If the number of carbons exceeds 24, the detergency (or releasability, the same applies hereinafter) becomes worse. R², R^ThreeAnd R^FourIs H or a hydrocarbon group having 1 to 24 carbon atoms.¹The same thing is mentioned. R², R^ThreeAnd R^FourIf the number of carbons exceeds 24, the cleaning properties are deteriorated.
In the general formula (2), R^FiveExamples thereof include alkylene groups having 2 to 4 carbon atoms such as ethylene group, propylene group and butylene group. R^FiveIf the number of carbons exceeds 4, the detergency becomes worse. p is an integer of 1 to 6 (preferably 1 to 3), and if p exceeds 6, detergency deteriorates.
[0009]
Specific examples of (A7) organic alkali include salts of the following cations (1) to (5) with at least one hydrocarbon group bonded to a nitrogen atom and a hydroxide anion, and mixtures thereof.
[0010]
(1) Quaternary ammonium cation containing four hydrocarbon groups
Tetrahydrocarbyl ammonium containing four alkyl groups having 1 to 6 carbon atoms [e.g., tetramethylammonium, tetraethylammonium, tetra (n- or i-) propylammonium, tetra (n-, i- or t-) butyl Ammonium, tetrapentylammonium, tetrahexylammonium and the like]; tetrahydrocarbylammonium containing three alkyl groups having 1 to 6 carbon atoms [eg, trimethylheptylammonium, trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethyl Stearylammonium, trimethylbenzylammonium, triethylhexylammonium, triethyloctylammonium, triethylstearylammonium, triethyl Dimethylammonium, tributylammonium, tributyloctylammonium, trihexylstearylammonium, etc.]; tetrahydrocarbylammonium containing two alkyl groups having 1 to 6 carbon atoms [e.g., dimethyldioctylammonium, diethyldioctylammonium, dimethyldibenzyl Ammonium, etc.], tetrahydrocarbylammonium containing one alkyl group having 1 to 6 carbon atoms [e.g., methyltrioctylammonium, ethyltrioctylammonium, methyloctyldibenzylammonium, etc.]
[0011]
(2) Tertiary amine cation containing three hydrocarbon groups
Trihydrocarbylamine cation containing 3 alkyl groups having 1 to 6 carbon atoms [e.g., trimethylamine cation, triethylamine cation, tributylamine cation, etc.]; Trihydrocarbylamine cation containing 2 alkyl groups having 1 to 6 carbon atoms [ For example, a dimethyloctylamine cation, a dimethylstearylamine cation, a diethyloctylamine cation, a dibutyloctylamine cation, a dimethylbenzylamine cation, etc.]; a trihydrocarbylamine cation containing one alkyl group having 1 to 6 carbon atoms [for example, methyl Dioctylamine cation, ethyl dioctylamine cation, methyloctylbenzylamine cation, etc.]
[0012]
(3) Secondary amine cation containing two hydrocarbon groups
A dihydrocarbylamine cation [eg, dimethylamine cation, diethylamine cation, dibutylamine cation, dihexylamine cation, etc.] containing two alkyl groups having 1 to 6 carbon atoms; one alkyl group having 1 to 6 carbon atoms Dihydrocarbylamine cation [for example, methyloctylamine cation, ethyloctylamine cation, butyloctylamine cation, hexyloctylamine cation, methylstearylamine cation, methylbenzylamine cation, ethylbenzylamine cation, etc.]
(4) Primary amine cation containing one hydrocarbon group
Monohydrocarbyl (C1-6) amine cations, such as methylamine cation, ethylamine cation, butylamine cation, hexylamine cation, etc.
[0013]
(5) Cations containing oxyalkylene groups
(I) Cations having one oxyalkylene group [for example, hydroxyethyltrimethylamine cation, hydroxyethyltriethylamine cation, hydroxypropyltrimethylamine cation, hydroxypropyltriethylamine cation, hydroxyethyldimethylethylamine cation, hydroxyethyldimethyloctylamine cation, etc.]
(Ii) a cation having two oxyalkylene groups [eg, dihydroxyethyldimethylamine cation, dihydroxyethyldiethylamine cation, dihydroxypropyldimethylamine cation, dihydroxypropyldiethylamine cation, dihydroxyethylmethylethylamine cation, dihydroxyethylmethyloctylamine cation, bis (2-hydroxyethoxyethyl) octylamine cation, etc.]
(Iii) a cation having three oxyalkylene groups [for example, trihydroxyethylmethylamine cation, trihydroxyethylethylamine cation, trihydroxyethylbutylamine cation, trihydroxypropylmethylamine cation, trihydroxypropylethylamine cation, trihydroxyethyloctyl Amine cations etc.]
[0014]
Of the alkali component (A), (A1) and (A7) are preferred from the viewpoints of detergency and rinsing properties.
Of (A1), from the viewpoint of detergency, preferred are alkali metal hydroxides, and more preferred are sodium hydroxide and potassium hydroxide.
Among (A7), from the viewpoints of detergency and rinsing properties, the salts (1) and (2) are preferred, the salt (1) is more preferred, and an alkyl having 1 to 6 carbon atoms is particularly preferred. A tetraalkylammonium hydroxide containing four groups, most preferably tetramethylammonium hydroxide or tetraethylammonium hydroxide.
The above compounds can also be used as a mixture.
[0015]
In the present invention, (B) includes a diol (B1) having a molecular weight of 62 to 250 that does not contain a nitrogen atom, a 3 to 8 valent polyhydric alcohol (B2) having a molecular weight of 92 to 400 that does not contain a nitrogen atom, Number average molecular weight having two or more oxyalkylene groups (2 to 3 carbon atoms) [hereinafter abbreviated as Mn, measured by gel permeation chromatography (GPC)] 150 to 500 polyoxyalkylene glycol (B3) and these The mixture of 2 or more types is mentioned.
[0016]
As (B1), alkanediol (alkanediol having 2 to 8 carbon atoms: ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neo Pentyl glycol, etc.), alicyclic diols (C6-C15 diols: cyclohexane-1,2-, 1,3- and 1,4-diol, cyclopentane-1,2- and 1,3-diol, And hydrogenated bisphenol A) and diols having one ether group in the molecule (such as diethylene glycol and dipropylene glycol). The molecular weight of (B1) is preferably 62 or more and less than 150.
[0017]
  (B2) 3 to 8 valent aliphatic polyhydric alcohol (glycerin, trimethylol ethane, trimethylol propane, diglycerin, triglycerin, tetraglycerin, pentaglycerin, xylitol, sorbitol, sucrose, etc.) Etc.
[0018]
As (B3), an alkylene oxide (2 to 3 carbon atoms) adduct (added mole number 1 to 10 moles) of (B1), for example, triethylene glycol, tetraethylene glycol, polyoxyethylene glycol (number average molecular weight 400) , Polyoxyethylene / propylene (random addition and / or block addition) glycol and the like.
[0019]
Among (B), from the viewpoints of detergency and corrosion resistance, the alkanediol in (B1) and the diol having one ether group in the molecule, the trivalent to octavalent in (B2) And (B3) triethylene glycol and tetraethylene glycol, and more preferred are ethylene glycol, propylene glycol, diethylene glycol, glycerin, diglycerin and triethylene glycol.
[0020]
The content of (A) and (B) in the cleaning agent of the present invention is preferably 0.2 to 20% based on the total weight of the cleaning agent from the viewpoint of cleaning properties and corrosion resistance. More preferably, it is 0.5-10%, (B) becomes like this. Preferably it is 5-99.8%, More preferably, it is 20-85%. The weight ratio of (A) to (B) is preferably 1/99 to 50/50, more preferably 2/98 to 30/70, from the viewpoints of detergency and corrosion resistance.
[0021]
If necessary, a surfactant (C), a hydrophilic solvent (D), another additive (E) and / or water can be added to the cleaning agent of the present invention.
Examples of the surfactant (C) include a nonionic surfactant (C1), an anionic surfactant (C2), a cationic surfactant (C3), an amphoteric surfactant (C4), and a mixture thereof.
[0022]
Examples of (C1) include alkylene oxide addition type nonionic surfactants [higher alcohols (8 to 18 carbon atoms), alkylphenols (10 to 24 carbon atoms), higher fatty acids (12 to 24 carbon atoms) or higher alkylamines. Direct addition of alkylene oxide [carbon number 2 to 4, for example, ethylene oxide (hereinafter abbreviated as EO), propylene oxide, butylene oxide, the same shall apply hereinafter) (molecular weight 158 to Mn 200,000) A polyoxyalkylene glycol (molecular weight 150 to Mn 6,000) reacted with a higher fatty acid (carbon number 12 to 24) or the like; a diol [exemplified as (B1) above] or a polyhydric alcohol [above (B2) Higher fatty acid (carbon number 12-24) A product obtained by adding an alkylene oxide to an esterified product obtained by reacting an aldehyde (molecular weight 250 to Mn 30,000), a product obtained by adding an alkylene oxide to a higher fatty acid (carbon number 8 to 24) amide (molecular weight 200 to Mn 30, 000), polyhydric alcohol (the above), alkyl (carbon number 8 to 60) ether added with alkylene oxide (molecular weight 120 to Mn 30,000), etc.], and polyhydric alcohol (carbon number 3 to 20) Type nonionic surfactants [polyhydric alcohol fatty acid (carbon number 8 to 60) ester, polyhydric alcohol alkyl (carbon number 8 to 60) ether, fatty acid (carbon number 8 to 60) alkanolamide and the like] and the like.
[0023]
Examples of (C2) include carboxylic acids (saturated or unsaturated fatty acids having 8 to 22 carbon atoms) or salts thereof, salts of carboxymethylates [aliphatic alcohols having 8 to 16 carbon atoms and / or EO (1 to 10 mol) salts of carboxymethylated products such as adducts, etc.], sulfate esters [higher alcohol sulfate esters (such as sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms)], higher alkyl ether sulfate esters [ EO (1-10 mol) adduct sulfate of aliphatic alcohol having 8 to 18 carbon atoms], sulfated oil (natural unsaturated fat or salt obtained by sulfating and neutralizing unsaturated wax as it is), Sulfated fatty acid ester (a salt obtained by sulfating and neutralizing a lower alcohol ester of an unsaturated fatty acid), sulfated olefin (olefin having 12 to 18 carbon atoms) Oxidized and neutralized salts), sulfonates [alkylbenzene sulfonate, alkylnaphthalene sulfonate, sulfosuccinic acid diester type, α-olefin (carbon number 12 to 18) sulfonate, Igepon T type, etc.] and phosphorus Acid ester salt [higher alcohol (carbon number 8 to 60) phosphate ester salt, higher alcohol (carbon number 8 to 60) EO adduct phosphate ester salt, alkyl (carbon number 4 to 60) phenol EO adduct phosphate ester Salt, etc.].
Examples of the salt include alkali metal (sodium, potassium, etc.) salt, alkaline earth metal (calcium, magnesium, etc.) salt, ammonium salt, alkylamine (C1-20) salt and alkanolamine (C2-12). For example, mono-, di- and triethanolamine) salts.
[0024]
(C3) includes quaternary ammonium salt type [tetraalkyl (4 to 100 carbon atoms) ammonium salt such as lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide; 3-80) benzylammonium salts, such as lauryldimethylbenzylammonium chloride (benzalkonium chloride); alkyl (2-60 carbons) pyridinium salts, such as cetylpyridinium chloride; polyoxyalkylene (2-4 carbons) tri Alkyl ammonium salts such as polyoxyethylene trimethyl ammonium chloride; sapamine type quaternary ammonium salts such as stearamide ethyl diethyl methyl Ammonium methosulphate], amine salt type [aliphatic higher amines (12 to 60 carbon atoms, such as laurylamine, stearylamine, cetylamine, hardened tallow amine, rosinamine, etc.) Salt or organic acid (C2-C22, for example, acetic acid, propionic acid, lauric acid, oleic acid, benzoic acid, succinic acid, adipic acid, azelaic acid) salt; higher fatty acid (lower C1-C11) fatty acid ( C12-24, e.g., stearic acid, oleic acid) salts; inorganic acid (above) salts or organic acid (above) salts such as EO adducts of aliphatic amines (C1-30); 3 Inorganic acids (such as triethanolamine monostearate, stearamide ethyl diethylmethylethanolamine, etc.) ) Salts or organic acids (above one) salts], and others.
[0025]
Examples of (C4) include amino acid type amphoteric surfactants [higher alkylamine (carbon number 12 to 18) sodium propionate and the like], betaine type amphoteric surfactants [alkyl (carbon number 12 to 18) dimethyl betaine, alkyl ( Carbon number 12-18) dihydroxyethyl betaine, coconut oil fatty acid amide propyl betaine, etc.], sulfate ester type amphoteric surfactant [higher alkyl (carbon number 8-18) amine sulfate ester sodium salt, hydroxyethyl imidazoline sulfate sodium salt Salt], sulfonate-type amphoteric surfactant (pentadecylsulfotaurine, imidazoline sulfonic acid, etc.), phosphate ester-type amphoteric surfactant [glycerin higher fatty acid (carbon number 8-22) esterified phosphoric acid Ester amine salts] and the like.
[0026]
Among (C1) to (C4), (C1) and (C2) are preferable from the viewpoints of detergency and corrosion resistance, and (C1) is more preferable. The amount of (C) used is usually 30% or less, preferably 1 to 20%, based on the total weight of the cleaning agent.
[0027]
As the hydrophilic solvent (D), solubility in water at 20 ° C. (g / 100 gH₂O) is 3 or more, water-soluble glycol ethers (D1) having one hydroxyl group or no hydroxyl group in the molecule, and water-soluble amide (D2).
[0028]
(D1)
(D11); an alkyl (carbon number 1-4) ether of ethylene glycol, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether,
(D12); alkyl (C1-C4) ethers of diethylene glycol, such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether;
(D13); alkyl ethers of mono or dipropylene glycol or triethylene glycol (1 to 4 carbon atoms), such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether and triethylene glycol monoethyl ether;
(D14); other glycol ethers such as 3-methyl-3-methoxy-1-butanol,
(D15); alkyl (C1-4) esters of (D11), such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate,
(D16); alkyl (C1-4) esters of (D12), such as diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate,
(D17); alkyl (C1-4) esters of (D13), such as propylene glycol monomethyl ether acetate and triethylene glycol monoethyl ether acetate,
(D18); alkyl (C1-4) esters of (D14), such as 3-methyl-3-methoxy-1-butanol acetate.
Among (D1), (D12), (D13), (D14) and (D18) are preferable from the viewpoints of detergency, rinseability and corrosion resistance. More preferred are diethylene glycol monobutyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether, (D14) and (D18) of (D12).
[0029]
Examples of (D2) include 2-pyrrolidone and N-alkyl (C1-3) -2-pyrrolidone. Of these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, Nn-propyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, and More preferred is N-methyl-2-pyrrolidone. (D1) and (D2) may be used alone or in combination of two or more. Of these, (D2) is preferred.
The amount of (D) to be used is preferably 30% or less, more preferably 1 to 20%, from the viewpoints of detergency, rinse and corrosion resistance, based on the total weight of the detergent.
[0030]
The amount of water used is preferably 94.8% by weight or less, more preferably 1 to 60% by weight, particularly preferably 2 based on the total weight of the cleaning agent from the viewpoints of cleaning properties, rinsing properties and corrosion resistance. ~ 30% by weight.
[0031]
(E) includes rust inhibitors [EO (2 to 10 mol) adducts of amines (having 6 to 30 carbon atoms, such as cyclohexylamine, laurylamine, stearylamine), chromate, nitrite, amine (carbon 6-30) higher fatty acid (carbon number 8-30) salt, alkali metal (sodium, potassium, etc.) salt of dicarboxylic acid (carbon number 12-24), alkanolamide of dicarboxylic acid (carbon number 12-24) ( For example, dodecenyl succinic acid diethanolamide), alkanolamide alkali metal salt of dicarboxylic acid (carbon number 12 to 24) (for example, dodecenyl succinic acid diethanolamide sodium salt)], antioxidant [phenol compound (2,6-di-t -Butyl-4-methylphenol), sulfur-containing compounds (dilaurylthiodipropionate, etc.) , Amine compounds (such as octyl diphenylamine), and a phosphorus compound (such as triphenyl phosphite)], sequestering agents (sodium ethylenediamine tetraacetate, sodium citrate), and the like.
The amount of (E) used is usually 20% or less, preferably 0.5 to 10% for the rust inhibitor, and usually 5% or less, preferably 0.1 to 10% for the antioxidant based on the total weight of the detergent. 1%, sequestering agent is usually 20% or less, preferably 0.5 to 10%.
[0032]
The viscosity of the cleaning agent of the present invention at 25 ° C. is usually 2 to 300 mm.²/ S, preferably from 3 to 100 mm from the viewpoint of detergency and rinsability²/ S, more preferably 4 to 50 mm²/ S. The viscosity can be measured with a viscometer such as Ostwald or Ubbelohde.
The pH (10% aqueous solution) of the cleaning agent of the present invention is usually from 10 to 14, and preferably from 10.5 to 13.5 from the viewpoints of cleaning properties and corrosion resistance.
[0033]
The use to which the cleaning agent of the present invention can be applied is not particularly limited, and can be widely used for cleaning electronic parts and the like in which aluminum is used for some or all of the parts. For example, glass substrates for liquid crystal panels (cleaning before alignment film patterning, peeling cleaning of defective alignment films), printed boards, plasma display glass substrates, electronic components such as thermal heads, air conditioner cooling fins, air cleaner aluminum electrode plates, Examples include electric parts such as electric razor blades, aluminum building materials, and the like. Examples of the cleaning object (dirt) include organic substances such as oil, fingerprints, resins, and organic particles, and inorganic substances such as inorganic particles (for example, glass powder, ceramic powder, and metal powder). Among these, the cleaning agent of the present invention is particularly preferably used for cleaning a glass substrate for a liquid crystal panel (cleaning of the glass substrate before thinning the alignment film, cleaning of the glass substrate in which the alignment film becomes defective). Can do.
[0034]
For example, as a method for peeling and cleaning the alignment film of the glass substrate for a liquid crystal panel using the cleaning agent of the present invention, a cleaning method using ultrasonic cleaning, shower cleaning, spray cleaning, dipping, immersion rocking, and a combination thereof is applied. it can. The washing temperature is usually about 10 to 70 ° C, preferably about 15 to 60 ° C. The washing time is usually 0.2 to 120 minutes, preferably 0.5 to 30 minutes. The rinsing temperature with water is usually from 5 to 90 ° C., preferably from 10 to 70 ° C. As the rinsing method, the same method as the above washing method can be applied. After rinsing, a clean glass substrate for a liquid crystal panel is obtained by heating and drying at 50 to 150 ° C., preferably 60 to 100 ° C. for 1 to 120 minutes, preferably 3 to 60 minutes, and can be reused.
[0035]
【Example】
Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. In the following, parts and% indicate parts by weight and% by weight.
First, the composition of the cleaning agent components used in the examples and comparative examples, the cleaning test, and the corrosion test method are shown.
[0036]
1. Composition of cleaning ingredients
A1-1: Sodium hydroxide (20% aqueous solution)
A1-2: Potassium hydroxide (20% aqueous solution)
A7-1: Tetramethylammonium hydroxide (15% aqueous solution)
A7-2: Tetraethylammonium hydroxide (15% aqueous solution)
A7-3: Tetra-n-butylammonium hydroxide
B1-1: Ethylene glycol
B1-2: propylene glycol
B1-3: Diethylene glycol
B2-1: Glycerin
B2-2: Diglycerin
B3-1: Triethylene glycol
C1-1: EO 9 mol adduct of higher alcohol (mixture of 16 to 18 carbon atoms)
C2-1: Sodium salt of di-2-ethylhexyl sulfosuccinate
(70% aqueous solution)
D2-1: N-methyl-2-pyrrolidone
Anticorrosive agent-1: EO2 molar adduct of cyclohexylamine
Rust inhibitor-2: dodecenyl succinic acid diethanolamide sodium salt
[0037]
2. Alignment film peelability
A glass substrate test in which a semi-fired vertically oriented polyimide film (film thickness 1 μm) is adhered by applying a polyimide resin on an ITO film (indium tin oxide film) formed in advance on a glass substrate and baking at 80 ° C. Create a piece (25 x 25 mm, thickness 0.75 mm), immerse it in a cleaning agent (25 ° C) for a specified time, place the test piece on a stainless steel basket, rinse with ion-exchanged water for 1 minute, and then backside The same aspect was rinsed. Next, the test piece was dried in a circulating dryer at 70 ° C. for 10 minutes and then observed with a microscope to evaluate the alignment film peelability in the following five stages.
[0038]
3. Corrosive
A glass substrate test piece (25 × 25 mm, thickness 0.75 mm) to which an aluminum thin film (thickness 0.1 μm) is adhered is immersed in a cleaning agent (25 ° C.) for a predetermined time, and the aluminum thin film is completely removed and the test piece is transparent. The time taken to become the corrosion time was measured. The longer the corrosion time, the better the corrosion resistance.
[0039]
Examples 1-13, Comparative Examples 1-3
Tables 1 and 2 show the formulation and performance evaluation results of the detergent.
[0040]
[Table 1]
[0041]
[Table 2]
[0042]
As shown in Comparative Example 1 in Table 1, the semi-fired vertical alignment polyimide film cannot be peeled only by the release solvent (N-methyl-2-pyrrolidone: release solvent for semi-fired horizontal alignment polyimide film). In addition, as shown in Comparative Example 2, when an alkaline agent is used in combination with this solvent, the peelability of the alignment film is improved, but the corrosion resistance is extremely deteriorated (corrosion time is 3 minutes), and a rust inhibitor is added. However, the corrosion resistance is not improved so much (Comparative Example 3) and it cannot withstand actual use.
The cleaning agents according to the present invention described in Tables 1 and 2 (Examples 1 to 13) can peel the semi-fired vertically-aligned polyimide film in 1 to 2 minutes, and the corrosion time is very long as 2 hours or more. It is good and can be used without problems.
[0043]
【The invention's effect】
Since the cleaning agent of the present invention is excellent in aluminum corrosion resistance, for example, the semi-fired vertically-aligned polyimide film can be peeled and cleaned in a short time without damaging the aluminum wiring of the glass substrate for liquid crystal panels and the color filter member. . Therefore, in the alignment film peeling and cleaning process (glass substrate regeneration process), not only the regeneration of the conventional glass substrate but also the aluminum wiring and the color filter member can be simultaneously recycled.
In addition, since the cleaning agent of the present invention is also excellent in the ability to remove oil, fingerprints, resins and particles, not only for electronic parts such as glass substrates for liquid crystal panels, but also for electrical parts, metal parts, building materials, etc. It can be applied to applications and is extremely useful.

Claims (6)

It consists of an organic alkali (A7) represented by the general formula (1) and a 3- to 8-valent aliphatic polyhydric alcohol (B2) having a molecular weight of 92 to 400 that does not contain a nitrogen atom. An alkali cleaning agent for stripping an alignment film of a liquid crystal panel, wherein the weight ratio with the polyhydric alcohol (B2) is from 1/99 to 50/50.
[Wherein, R ¹ is a hydrocarbon group having 1 to 24 carbon atoms, R ² , R ³ and R ⁴ are H, a hydrocarbon group having 1 to 24 carbon atoms, or a group represented by the general formula (2), respectively. R ⁵ represents an alkylene group having 2 to 4 carbon atoms, and p represents an integer of 1 to 6. ]   The cleaning agent according to claim 1, wherein the organic alkali (A7) is tetraalkyl (C1-4) ammonium hydroxide.   The cleaning agent according to claim 1 or 2, wherein the aliphatic polyhydric alcohol (B2) is glycerin or diglycerin. Further, surfactant (C), water-soluble glycol ethers (D1) having one hydroxyl group or no hydroxyl group in the molecule (D1), water-soluble amide (D2) , other additives (E) and / or water are added. The cleaning agent according to any one of claims 1 to 3, which is added.   The amount of water based on the total weight of the cleaning agent is 2 to 30%, and the cleaning agent according to any one of claims 1 to 4. 6. A liquid crystal panel , wherein the cleaning agent according to claim 1 is cleaned by at least one method selected from ultrasonic cleaning, shower cleaning, spray cleaning, immersion and immersion rocking. Cleaning method for glass substrates using aluminum.