JP2006233029A - Alkaline detergent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkaline detergent which has an excellent non-corrosivity to aluminum, since the conventional alkaline detergents easily corrode non-ferrous metals such as aluminum and therefore are unable to be used for cleaning electronic parts at least for a portion of which aluminum is used. <P>SOLUTION: The alkaline detergent contains (A) an organic alkali and (B) one or more than one kind of hydrophilic organic solvent selected from the group consisting of water, (B1) a monool with a molecular weight of ≥32 to a number average molecular weight of 500, (B2) a diol with a molecular weight of ≥62 to a number average molecular weight of 250, (B3) a 3-9 valent polyol with a molecular weight of ≥92 to a number average molecular weight of 400 and (B4) an alkyl ether of (B1) or (B2). The content of an alkali metal or an alkaline earth metal of the alkaline detergent is ≤1,000 ppm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an alkaline cleaner used to remove oils and fats, resins, inorganic particles and the like adhering to electronic parts, electric parts, aluminum building materials and the like. More specifically, the present invention relates to an alkali cleaning agent used as a stripping solution for a vertically aligned polyimide film (particularly a semi-baked film) of a liquid crystal panel.

  Conventionally, alkaline detergents have been widely used in production sites for electronic parts, electrical parts, aluminum building materials and the like because they are superior in ability to remove oils, fats, resins, inorganic particles, and the like compared to neutral detergents.

  However, since the alkaline cleaning agent easily corrodes non-ferrous metals such as aluminum, it cannot be used for cleaning electronic parts and the like in which aluminum is used for at least a part of the parts. For example, polyimide alignment films for electronic parts, particularly liquid crystal panels, tend to increase in number of vertical alignment type polyimide alignment films in place of conventional horizontal alignment types as the demand for liquid crystal panels with a wide viewing angle increases. If the horizontal alignment type is a semi-baked state (semi-cured film desolvated at about 80 ° C.) before complete baking (baking temperature: about 180 ° C.), the defective product is an aluminum thin film (N-methylpyrrolidone) with a solvent such as N-methylpyrrolidone. The alignment film can be peeled off without corroding the wiring), but in the case of the vertical alignment type, since the alignment film cannot be peeled off with a solvent even in a semi-baked state, peeling with an alkaline cleaner is performed ( For example, see Patent Document 1). At that time, since the aluminum thin film (wiring) on the glass substrate is corroded, the aluminum thin film portion is protected with wax or the like and then washed, and then the wax is removed with a solvent such as hydrocarbon to regenerate the glass substrate, or orientation. At the same time as the film, the aluminum thin film (wiring) was completely peeled and dissolved, and then only the glass substrate was regenerated.

JP-A-6-306661

  An object of the present invention is to provide an alkaline cleaner excellent in non-corrosiveness of aluminum, a cleaning method, a cleaned electronic component, and the like.

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 (A), water, a monool (B1) having a molecular weight of 32 to a number average molecular weight of 500, a diol (B2) having a molecular weight of 62 to a number average molecular weight of 250, a molecular weight of 92 to a number average molecular weight of 400. Containing one or more hydrophilic organic solvents (B) selected from the group consisting of 3 to 9-valent polyols (B3) and alkyl ethers (B4) of (B1) or (B3), and an alkali metal Or an alkaline detergent having an alkaline earth metal content of 1,000 ppm or less; using the detergent, selected from the group consisting of ultrasonic, shower, spray, immersion and immersion rocking cleaning Cleaning method of electronic parts, electric parts or aluminum building materials characterized by cleaning by one or more kinds of methods; washing, rinsing, drying Electronic components obtained by, is an electrical component or aluminum building materials.

The alkaline cleaner of the present invention has the following effects.
(1) Excellent aluminum non-corrosiveness.
(2) The semi-fired vertically aligned polyimide film can be peeled and washed in a short time without damaging the aluminum wiring and color filter member of the glass substrate for liquid crystal panel.
(3) 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 regenerated and used simultaneously.
(4) Excellent ability to remove oil, fingerprint, resin and inorganic particles.

  The organic alkali (A) in the present invention includes the following (A1) to (A5) and mixtures thereof.

(A1) Hydroxylamine [carbon number (hereinafter abbreviated as C) 2-22]
Monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, N, N-dimethylethanolamine and the like;

(A2) Monoamine (C1-24)
Aliphatic amines [primary amines (ethylamine, butylamine, laurylamine, etc.), secondary amines (diethylamine, dibutylamine, etc.), tertiary amines (trimethylamine, triethylamine, etc.), alicyclic amines [primary amine (cyclohexyl) Amines, etc.), secondary amines (dicyclohexylamine, etc.)], heterocyclic amines [secondary amines (morpholine, piperidine, 2-pipecoline, etc.), tertiary amines (N-methylpiperidine, N-methylmorpholine, etc.), etc. ] And aromatic ring-containing amines [primary amines (aniline, benzylamine, etc.), secondary amines (N-methylaniline, etc.), tertiary amines (N-dimethylaniline, pyridine, quinoline, etc.), etc.];

(A3) Polyamine (C2-18)
(A3-1) Aliphatic polyamine (C2-18)
C2-6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-6) polyamine [diethylenetriamine, iminobispropylaminebis (hexamethylene) triamine, triethylene Tetramine, tetraethylenepentamine, pentaethylenehexamine, etc.], alkyl (C1-4) or hydroxyalkyl (C2-4) substitution products thereof [dialkyl (C1-3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanol Amine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, etc.], alicyclic or heterocyclic-containing aliphatic polyamine [3,9-bis (3-amino) Propyl) -2,4,8,10-spiro [5,5] undecane] and the like (A3-2) alicyclic polyamines (C4～15)
1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc. (A3-3) heterocyclic polyamine (C4-15)
Piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, etc. (A3-4) Aromatic ring-containing polyamine (C6-20)
Non-nuclear substituted aromatic ring-containing polyamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), benzidine , Thiodianiline, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, naphthylenediamine, etc.], containing an aromatic ring having a nucleus-substituted alkyl group (C1-4) Polyamines [2,4- and 2,6-tolylenediamine, diethyltolylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 1,3-dimethyl-2,4-diaminobenzene, 1, 3-dimethyl-2,6-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-trie 2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl-1 , 4-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, etc.] Aroma having a secondary amino group Ring-containing polyamine [in which part or all of —NH ₂ of the above aromatic ring-containing polyamine is substituted with —NH—R (where R is a C 1-4 lower alkyl group such as methyl, ethyl, etc.) [4, 4 '-Di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene and the like]];

(A3-5) Other polyamines [number average molecular weight [hereinafter abbreviated as Mn. Measurement is by gel permeation chromatography (GPC)] 200-2,000]
Polyether polyamine [hydride of cyanoethylated product of polyether polyol (polyalkylene glycol, etc.), polyethyleneimine, polyvinylamine, poly (di) allylamine, etc .;

(A4) Compound containing amidine skeleton Guanidine compound [guanidine, methylguanidine, tetramethylguanidine, ethylguanidine, 1,3,4,6,7,8-hexahydro-2H-pyrimido [1,2-a] pyrimidine, 1,3,4,6,7,8-hexahydro-1-methyl-2H-pyrimido [1,2-a] pyrimidine etc.], cyclic and acyclic amidine compounds [1,8-diazabicyclo [5,4 , 0] undecene-7,1,6-diazabicyclo [4,3,0] nonene-5 etc.] and the like;

(A5) Organic alkali represented by the following general formula (1)

In the formula, each of R ¹ , R ² , R ³ and R ⁴ is the same or different and is represented by C1-24, preferably 1-14 hydrocarbon group or — (A ¹ O) _p H. A ¹ represents a C2-4 alkylene group, and p represents an integer of 1-6.
Examples of the C1-24 hydrocarbon group include linear or branched aliphatic saturated or unsaturated hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic ring-containing hydrocarbon groups.
As the linear or branched aliphatic saturated hydrocarbon group, an alkyl (methyl, ethyl, n-, i-, sec- and t-butyl, octyl, 2-ethylhexyl, octadecyl, etc.) group; linear or branched As the aliphatic unsaturated hydrocarbon group, an alkenyl (vinyl, propenyl, allyl, butenyl, etc.) group; an alicyclic hydrocarbon group, a cycloalkyl group (cyclohexyl group, etc.); an aromatic ring-containing hydrocarbon group as An aryl (phenyl, naphthyl, etc.) group, an aralkyl (benzyl, phenethyl, etc.) group, an alkylaryl (methylphenyl, ethylphenyl, nonylphenyl, methylnaphthyl, ethylnaphthyl) group and the like.
Of these hydrocarbon groups, a linear or branched aliphatic hydrocarbon group is preferable from the viewpoint of detergency, and an alkyl group and an alkenyl group are more preferable.
When C of R ^{1 to} R ⁴ is 24 or less, the cleaning property (or peelability, the same applies hereinafter) is excellent.

In the formula, examples of A ¹ include C2-4 alkylene groups such as an ethylene group, a propylene group, and a butylene group.
When C of A ¹ is 4 or less, the detergency is good. p is an integer of 1 to 6 (preferably 1 to 3), and if p is 6 or less, the detergency is good.

Examples of the cation in the general formula (1) include tetrahydrocarbyl ammonium cations of the following [1] to [4], ammonium cations having an oxyalkylene group of the following [5], and mixtures thereof.
[1] A cation containing four C1-6 alkyl groups Tetramethylammonium, tetraethylammonium, tetra (n- and i-) propylammonium, tetra (n-, i- and t-) butylammonium, tetrapentylammonium, Tetrahexylammonium, trimethylethylammonium, tetraethylammonium and the like;
[2] Cation containing three C1-6 alkyl groups and one C7-24 hydrocarbyl group Trimethylheptylammonium, trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethylstearylammonium, trimethylbenzylammonium , Triethylhexylammonium, triethyloctylammonium, triethylstearylammonium, triethylbenzylammonium, tributylammonium, tributyloctylammonium, trihexylstearylammonium and the like;
[3] Cations containing two C1-6 alkyl groups and two C7-24 hydrocarbyl groups, such as dimethyldioctylammonium, diethyldioctylammonium and dimethyldibenzylammonium;
[4] Cations containing one C1-6 alkyl group and three C7-24 hydrocarbyl groups, such as methyltrioctylammonium, ethyltrioctylammonium and methyloctyldibenzylammonium;

[5] Ammonium having oxyalkylene group (i) Cation having one oxyalkylene group Hydroxyethyltrimethylammonium, hydroxyethyltriethylammonium, hydroxypropyltrimethylammonium, hydroxypropyltriethylammonium, hydroxyethyldimethylethylammonium and hydroxyethyldimethyloctyl Ammonium and the like;
(Ii) Cations having two oxyalkylene groups Dihydroxyethyldimethylammonium, dihydroxyethyldiethylammonium, dihydroxypropyldimethylammonium, dihydroxypropyldiethylammonium, dihydroxyethylmethylethylammonium, dihydroxyethylmethyloctylammonium and bis (2-hydroxyethoxyethyl) ) Octyl ammonium, etc.
(Iii) Cations having three oxyalkylene groups Trihydroxyethylmethylammonium, trihydroxyethylethylammonium, trihydroxyethylbutylammonium, trihydroxypropylmethylammonium, trihydroxypropylethylammonium, trihydroxyethyloctylammonium and the like;

  Of the cations in general formula (1), tetrahydrocarbylammonium is preferred from the viewpoints of detergency and rinsability, more preferred are [1] and [2] above, and [1] is most preferred. Preference is given to tetramethylammonium, tetraethylammonium and combinations thereof.

(B1) in the present invention includes a C1-12 aliphatic alcohol, a C3-12 alicyclic alcohol, a C6-12 aromatic ring-containing alcohol, an alkylene oxide of these alcohols (hereinafter abbreviated as AO) [C2 -4, for example, ethylene oxide (hereinafter abbreviated as EO), propylene oxide, butylene oxide, and so on. And adducts and mixtures thereof.
Examples of the C1-12 aliphatic alcohol include methanol, ethanol, n- and i-propanol, and n-, i-, sec- and t-butanol. Examples of the AO adduct of the alcohol include ethylene glycol monomethyl ether, Examples include diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether.
Examples of the C3-12 alicyclic alcohol include cyclohexanol and 2-methylcyclohexanol. Examples of the AO adduct of the alcohol include ethylene glycol cyclohexyl ether, diethylene glycol cyclohexyl ether, and propylene glycol cyclohexyl ether. .
Examples of the C6-12 aromatic ring-containing alcohol include benzyl alcohol, and examples of the AO adduct of the alcohol include an AO 1-5 mol adduct of benzyl alcohol. The alcohols also include AO adducts of phenolic compounds [C6-20, such as phenol, o-, m- and p-cresol], such as ethylene glycol monophenyl ether and diethylene glycol monophenyl ether.
Of these, ethylene glycol monomethyl ether, triethylene glycol monomethyl ether, and more preferably diethylene glycol monomethyl ether are preferable from the viewpoint of detergency and aluminum non-corrosiveness.

  The molecular weight of (B1) is a molecular weight of 32 to Mn500, preferably a molecular weight of 56 to Mn400, more preferably a molecular weight of 76 to Mn350. Those having a molecular weight of less than 32 do not exist, and if Mn exceeds 500, the cleaning properties and rinsing properties deteriorate.

In the present invention, (B2) includes alkanediol (C2-8, such as ethylene glycol, 1,2- and 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol). , Cycloaliphatic diols (C6-15, eg cyclohexane-1,2-, 1,3- and 1,4-diol, cyclopentane-1,2- and 1,3-diol and hydrogenated bisphenol A), molecules Diols having one ether group therein (C2-8, such as diethylene glycol and dipropylene glycol), and mixtures thereof are included.
Of these, diethylene glycol is preferable from the viewpoint of detergency and non-corrosive aluminum, and ethylene glycol and propylene glycol are more preferable.

  The molecular weight of (B2) is a molecular weight of 62 to a number average molecular weight of 250, preferably a molecular weight of 62 to 150, and more preferably a molecular weight of 62 to Mn120. Those having a molecular weight of less than 62 do not exist, and if Mn exceeds 250, the detergency and rinsing properties deteriorate.

In the present invention, (B3) includes 3 to 9 valent polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and Dipentaerythritol, 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin, triglycerin and other polyglycerins, etc.], saccharides and derivatives thereof (eg sucrose, glucose, fructose, mannose) , Lactose, and glycoside (such as methyl glucoside)], and AO adducts thereof (addition mole number: 1 to 7 mol).
Of these, diglycerin, triglycerin and xylitol are preferred from the viewpoints of detergency and rinsing properties, and glycerin and sorbitol are more preferred.

  The molecular weight of (B3) is a molecular weight of 92 to Mn400, preferably a molecular weight of 92 to Mn350, and more preferably a molecular weight of 92 to Mn300. Those having a molecular weight of less than 92 do not exist, and when Mn exceeds 400, the rinsing property is deteriorated.

(B4) in the present invention is an alkyl (C1-8, preferably 1-2) ether of (B1) or (B3).
Examples of (B4) include (B1) alkyl ethers (B4-1) and (B3) mono- and poly (divalent to 9-valent) alkyl ethers (B4-2).
(B4-1) is represented by the following general formula (2).

^{R 5 O (A 1 O)} n -R 6 (2)

[Wherein, R ⁵ and R ⁶ are the same or different C1-8 hydrocarbon groups, A ¹ is the same as above, and n is an integer of 1-4. ]
Specific examples of (B4-1) include diethylene glycol dimethyl- and diethyl ether, triethylene glycol dimethyl- and diethyl ether.
Among (B4-2), as monoalkyl ether, glycerol monomethyl ether, diglycerol monomethyl ether, sorbitol monomethyl ether, etc., and as dialkyl ether, glycerol 1,2-dimethyl ether, glycerol 1,3-dimethyl ether, glycerol 1,3 Examples of diethyl ether and glycerin 1-ethyl-2-propyl ether, and poly (trivalent to 9-valent) alkyl ethers include those in which a corresponding number of hydroxyl groups are substituted with alkyl ether groups.
Of these, diethylene glycol dimethyl ether is preferable from the viewpoint of detergency and non-corrosive aluminum, and diethylene glycol diethyl ether is more preferable.

Of the above (B), preferred from the viewpoints of detergency and non-corrosive aluminum are (B2) / (B3), (B1) / (B3) / (B4), and more preferably This is a combination of (B1) / (B3).
When used in combination, the weight ratio of the sum of (B1), (B2) and (B4) to (B3) is preferably 70 to 99/1 to 30, more preferably from the viewpoint of detergency and non-corrosive aluminum. Is 80-98 / 2-20.

  It does not specifically limit as water in this invention, Any of ion-exchange water, a tap water, or distilled water may be sufficient. When tap water is used, the content of alkali metal or alkaline earth metal is preferably 100 ppm or less, respectively.

The ratio of (A), water and (B) based on the total weight of the alkaline cleaner of the present invention is preferably 0.1 to 25% from the viewpoint of detergency and non-corrosive aluminum, Preferably 0.2 to 15%, water is preferably 2 to 50%, more preferably 3 to 40%, (B) is preferably 11 to 95%, more preferably 20 to 90%.
The ratio of (B1) to (B4) based on the weight of (B) is preferably (B1) is 10 to 90%, more preferably 15 to 85%, and (B2) is preferably 0 to 80%. %, More preferably 0-70%, (B3) is preferably 1-20%, more preferably 2-15%, and (B4) is preferably 0-50%, more preferably 0-40%.

  In addition to (A), (B) and water, the cleaning agent of the present invention may further contain other hydrophilic organic solvent (C), surfactant (D) and other additives (E) as necessary. May be.

Examples of other hydrophilic organic solvents (C) include various solvents such as nitrogen atom-containing solvents [C5-12, such as pyrrolidone compounds (N-methylpyrrolidone, N-ethylpyrrolidone, 2-pyrrolidone, etc.), and formamide compounds ( N-methylformamide, N, N-dimethylformamide, etc.)]; Lactone [C3-12, such as propiolactone, butyrolactone]; Ketone [C3-12, such as methylethylketone, cyclohexanone, diacetone alcohol]; Cyclic ether [C3-3 12, for example tetrahydrofuran, tetrahydropyran]; esters [C3-12, for example ethyl acetate, ethyl lactate, butyl lactate, ethyl acetoacetate].
Of these, nitrogen atom-containing solvents and lactones are preferred, and N-methylpyrrolidone and butyrolactone are more preferred.
The content of (C) is usually 50% or less, preferably 10 to 30%, based on the total weight of the cleaning agent.

  Examples of the surfactant (D) include a nonionic surfactant (D1), an anionic surfactant (D2), a cationic surfactant (D3), an amphoteric surfactant (D4), and a mixture thereof. However, (D1) does not include the above (B), and (D3) does not include the organic alkali represented by the general formula (1).

  As (D1), AO addition type nonionic surfactant [higher alcohol (C8-18), alkylphenol (C10-24), higher fatty acid (C8-30, the same below) or higher alkylamine (C8-24), etc. Directly added with AO (Mn 158 to 200,000); polyoxyalkylene (Mn 150 to 6,000) reacted with a higher fatty acid or the like; diol [such as those exemplified as the above (B2)] or 3 A compound obtained by adding AO to an esterified product obtained by reacting a higher fatty acid with a hydroxyl group-containing compound such as a 9-valent polyol [as exemplified above for (B3)], a higher fatty acid amide To which AO is added (Mn 200 to 30,000), polyhydric alcohol (the above) alkyl (C8 to 60) AO added to AO (Mn120 to 30,000, etc.)] and polyhydric alcohol (C3-20) type nonionic surfactant [polyhydric alcohol fatty acid (C8-60) ester, polyhydric alcohol alkyl ( C8-60) ether, fatty acid (C8-60) alkanolamide, etc.] and the like.

Examples of (D2) include carboxylic acid (saturated or unsaturated fatty acid of C8-22) or a salt thereof, a salt of carboxymethylated product [addition of aliphatic alcohol of C8-16 and / or EO (1-10 mol) thereof. Salts of carboxymethylated products, etc.], sulfate esters [higher alcohol sulfate esters (such as C8-18 aliphatic alcohol sulfate salts)], etc., higher alkyl ether sulfate salts [C8-18 aliphatic] EO (1-10 mol) adducts of alcohol, etc.], sulfated oil (natural unsaturated oil or salt obtained by sulfating and neutralizing unsaturated wax as it is), sulfated fatty acid ester (unsaturated) A salt obtained by sulfating and neutralizing a lower alcohol ester of a fatty acid), a sulfated olefin (a salt obtained by sulfating and neutralizing an olefin of C12-18), Sulfonates [alkyl benzene sulfonate, alkyl naphthalene sulfonate, sulfosuccinic acid diester type, α-olefin (C12-18) sulfonate, Igepon T type, etc.] and phosphate ester salts [higher alcohol (C8-60) Phosphate ester salt, higher alcohol (C8-60) EO adduct phosphate ester salt, alkyl (C4-60) phenol EO adduct phosphate ester salt, etc.].
Examples of the salts include ammonium salts, alkylamine (C1-20) salts and alkanolamine (C2-12, for example, mono-, di- and triethanolamine) salts.

  (D3) is a quaternary ammonium halogen salt type [tetraalkyl (C4-100) ammonium chloride such as lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide; C3-80) benzylammonium chloride, such as lauryldimethylbenzylammonium chloride (benzalkonium chloride); alkyl (C2-60) pyridinium salts, such as cetylpyridinium chloride; polyoxyalkylene (C2-4) trialkylammonium chloride, such as poly Oxyethylenetrimethylammonium chloride; sapamine-type quaternary ammonium salts such as stearamide Tildiethylmethylammonium methosulfate], amine salt type [higher aliphatic amines (C12-60, such as laurylamine, stearylamine, cetylamine, hardened tallow amine, rosinamine) inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) Salts or organic acids (C2-22, such as acetic acid, propionic acid, lauric acid, oleic acid, benzoic acid, succinic acid, adipic acid, azelaic acid) salts; inorganics such as EO adducts of aliphatic amines (C1-30) Acid (above) salt or organic acid (above) salt; inorganic acid (above) salt or organic acid of tertiary amine (triethanolamine monostearate, stearamide ethyl diethyl methylethanolamine, etc.) And the like).

  Examples of (D4) include amino acid type amphoteric surfactant [higher alkylamine (C12-18) ammonium propionate, etc.], betaine type amphoteric surfactant [alkyl (C12-18) dimethylbetaine, alkyl (C12-18) Dihydroxyethyl betaine, coconut oil fatty acid amide propyl betaine, etc.], sulfate ester type amphoteric surfactant [sulfuric ester amine salt of higher alkyl (C8-18) amine, hydroxyethyl imidazoline sulfate amine amine etc.], sulfonate type Examples include amphoteric surfactants (pentadecyl sulfotaurine, imidazoline sulfonic acid, etc.), phosphate ester salt type amphoteric surfactants [phosphate ester amine salts of glycerol higher fatty acid (C8-22) esterified products], and the like.

Among (D1) to (D4), (D2) is preferable from the viewpoint of detergency and non-corrosive aluminum, and (D1) is more preferable.
The content of (D) is usually 30% or less, preferably 1 to 20%, based on the total weight of the cleaning agent.

Other additives (E) include rust inhibitors [amine (C6-30, for example, cyclohexylamine, laurylamine, stearylamine) EO (2-10 mol) adduct, chromate, nitrite, amine ( C6-30) higher fatty acid salt, dicarboxylic acid (C12-24) amine (monoethanolamine, diethanolamine etc.) salt, dicarboxylic acid (C12-24) alkanolamide (dodecenyl succinic acid diethanolamide etc.), dicarboxylic acid (C12) -24) alkanolamidoamine salts (such as dodecenyl succinic acid diethanolamide diethanolamine salts)], antioxidants [phenol compounds (2,6-di-t-butyl-4-methylphenol etc.), sulfur compounds (dilaurylthio) Dipropionate, etc.), phosphorus compounds (triphenylphos) Aito etc.), etc.], sequestering agents (ethylenediaminetetraacetic acid amine salts include citric acid amine salts, etc.) and the like.
The content of (E) 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%.
The total content of (C), (D) and (E) based on the weight of the cleaning agent of the present invention is usually 40% or less, preferably 30% or less, more preferably 20% or less.

  The cleaning agent of the present invention is produced by blending (A), water, (B) and, if necessary, (C) to (E), stirring and mixing. The order of blending is not particularly limited, and (A), (B) and water are first blended together, stirred and mixed, and then (C) to (E) are added if necessary, (A), (B ), Water, and if necessary, (C) to (E) may be mixed together and stirred and mixed.

  The content of alkali metal or alkaline earth metal in the cleaning agent of the present invention is 1,000 ppm or less, preferably 800 ppm or less, more preferably 0 to 500 ppm. If the content exceeds 1,000 ppm, the non-corrosiveness of aluminum deteriorates. The content of alkali metal or alkaline earth metal in the cleaning agent can be analyzed by any method such as atomic absorption analysis, plasma emission analysis, or fluorescent X-ray analysis.

The cleaning agent of the present invention is usually solid or liquid, and is preferably liquid from the viewpoint of ease of use, and in the case of liquid, it may be either transparent or cloudy. When the cleaning agent of the present invention is liquid, the viscosity (mm ² / s) at 25 ° C. is usually from 2 to 300, preferably from 3 to 100 mm ² / s, more preferably from 4 to 300, from the viewpoints of cleaning properties and rinsing properties. 50 mm ² / s. The viscosity can be measured with a viscometer such as Ostwald or Ubbelohde.
The pH of the cleaning agent of the present invention (10% by weight aqueous solution as the cleaning agent) is usually 10 to 14, and preferably 10.5 to 13.5 from the viewpoint of cleaning properties and aluminum non-corrosiveness.

For example, the 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 is one or two selected from the group consisting of ultrasonic, shower, spray, immersion, and immersion rocking cleaning. The above cleaning method can be applied.
The cleaning agent of the present invention at the time of washing may be further diluted with water if necessary, but is preferably within the above water content range.

  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 5 to 90 ° C., preferably 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 usually at 50 to 150 ° C., preferably 60 to 100 ° C. for 1 to 120 minutes, preferably 3 to 60 minutes, and can be reused.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this. In addition, a part shows a weight part below.

Examples 1-9, Comparative Examples 1-3
The cleaning agents of Examples and Comparative Examples were prepared by thoroughly stirring and mixing each component (indicated by pure content) shown in Table 1 in a 1 L beaker at room temperature.
Abbreviations in Table 1 are as follows.
A-1: Tetramethylammonium hydroxide A-2: Tetraethylammonium hydroxide A-3: Potassium hydroxide B1-1: Diethylene glycol monomethyl ether B1-2: Triethylene glycol monomethyl ether B2-1: Propylene glycol B2-2: Ethylene glycol B3-1: Glycerin B3-2: Sorbitol B4-1: Diethylene glycol diethyl ether

  The evaluation methods for the cleaning agents obtained in Examples and Comparative Examples are shown below, and the evaluation results are shown in Table 1.

1. Alignment film peelability A polyimide resin is applied on a glass substrate (25 × 25 mm, thickness 0.75 mm) on which an ITO film (indium tin oxide film) has been formed in advance, and the operation of baking at 80 ° C. is repeated three times. A glass substrate test piece in which a semi-fired vertically oriented polyimide film (film thickness 5 μm) was adhered was prepared. After immersing the test piece in a cleaning agent (25 ° C.) for a predetermined time, the test piece was placed on a stainless steel basket and rinsed with ion-exchanged water for 1 minute, and the back side was similarly 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.
<Evaluation criteria>
5: There is no alignment film on the glass substrate surface.
4: The trace of the alignment film remains on the glass substrate surface.
3: A little alignment film remains on a part of the glass substrate surface.
2: The alignment film remains on most of the glass substrate surface.
1: An alignment film remains on the entire surface of the glass substrate.

2. A glass substrate test piece (25 × 25 mm, thickness 0.75 mm) to which a corrosive aluminum thin film (thickness 0.1 μm) is adhered is immersed in a cleaning agent (40 ° C.) for a predetermined time, and the aluminum thin film is completely removed. Was measured as the time for the corrosion to become transparent. The longer the corrosion time, the better the non-corrosiveness of aluminum.

3. Measurement of Alkali Metal or Alkaline Earth Metal Content A plasma emission analysis was performed under the following measurement conditions.
<Measurement conditions>
Measuring instrument: ICPS-8000 [manufactured by Shimadzu Corporation]
Sample: The cleaning agents of Examples and Comparative Examples were diluted 10 times with 1% nitric acid aqueous solution.

  As shown in Table 1, the cleaning agents of the present invention (Examples 1 to 9) can release the semi-fired vertically-aligned polyimide film in 1 to 2 minutes, and have a corrosion time of 24 hours or more and aluminum non-corrosiveness. Very good.

  Since the cleaning agent of the present invention is excellent in non-corrosive aluminum, it is used for cleaning various electronic parts, electrical parts, aluminum building materials, etc., preferably cleaning electronic parts, particularly aluminum is used for at least a part of the parts. It can be widely used for cleaning electronic parts and the like. 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 object to be cleaned (dirt) include organic substances such as oil, fingerprints, resins, and organic particles, and inorganic substances such as inorganic particles (glass powder, ceramic powder, metal powder, and the like). Among these, the cleaning agent of the present invention is particularly suitable for cleaning a glass substrate for a liquid crystal panel (cleaning of a glass substrate before thinning the alignment film or cleaning of a glass substrate in which the alignment film becomes defective). Can be very useful.

Claims (9)

Organic alkali (A), water, monool (B1) having a molecular weight of 32 to number average molecular weight 500, diol (B2) having a molecular weight of 62 to number average molecular weight 250, and 3 to 9-valent polyol having a molecular weight of 92 to number average molecular weight of 400 (B3) and one or more hydrophilic organic solvents (B) selected from the group consisting of alkyl ethers (B4) of (B1) or (B3), and an alkali metal or alkaline earth metal Alkaline detergent characterized by content rate being 1,000 ppm or less. The alkaline cleaner according to claim 1, comprising 0.1 to 25% by weight of (A), 2 to 50% by weight of water, and 11 to 95% by weight of (B). ] The cleaning agent according to claim 1 or 2, wherein the weight ratio of the sum of (B1), (B2) and (B4) to (B3) is 70 to 99/1 to 30. The alkali cleaning agent according to claim 1, wherein (A) is a compound represented by the following general formula (1).

[Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a monovalent hydrocarbon group having 1 to 24 carbon atoms or — (A ¹ O) _PH]. Group, A ¹ represents an alkylene group having 2 to 4 carbon atoms, and p represents an integer of 1 to 6. ] Furthermore, the alkali cleaning agent in any one of Claims 1-4 formed by containing other hydrophilic organic solvents (C) other than (B), surfactant (D), and another additive (E). Washing | cleaning by the 1 type (s) or 2 or more types of methods chosen from the group which consists of ultrasonic, shower, spray, immersion, and immersion rocking | fluctuation washing | cleaning using the alkali cleaning agent in any one of Claims 1-5. Cleaning method for electronic parts, electrical parts and aluminum building materials. The cleaning method according to claim 6, wherein the electronic component is a glass substrate. The cleaning method according to claim 7, wherein the glass substrate is a glass substrate using aluminum at least in part. An electronic component, an electrical component, or an aluminum building material obtained by washing with the washing method according to claim 6, rinsing, and drying.