JP3255392B2 - Aqueous detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous detergent composition. More specifically, it is used in precision parts including metals such as aluminum, nickel, copper, zinc and tin, alloys such as brass, brass and solder, and easily corroded materials such as plated parts, or in an assembling process thereof. Excellent in removing dirt such as oils and fats, machine oil, cutting oil, grease, liquid crystal, rosin-based flux, etc. present on the solid surface of jigs and tools, and
The present invention relates to a water-based cleaning composition that does not corrode alloys and plated parts.

[0002]

2. Description of the Related Art
For removing dirt mainly composed of organic substances such as oils and fats present on the solid surfaces of precision parts and jigs, alcohol solvents such as ethyl alcohol and isopropyl alcohol; hydrocarbon solvents such as kerosene, benzene and xylene; trichloroethylene Solvent-based cleaning agents such as chlorine-based solvents such as tetrachloroethylene, and fluorocarbon-based solvents such as trichlorotrifluoroethane are used. In particular, chlorine-based solvents or chlorofluorocarbon-based solvents are used for components such as electronics, electricity, and machines, taking advantage of their high cleaning properties and flame retardancy.

[0003] However, alcohol solvents have safety problems, and hydrocarbon solvents, especially benzene, have a problem.
Xylene and the like are compounds having high toxicity and are designated as harmful substances for occupational safety and health, and it is not preferable to use them as cleaning agents in view of the danger and complexity of handling such substances. On the other hand, it has been clarified that cleaning agents using chlorine-based and chlorofluorocarbon-based solvents have serious problems in safety, toxicity, environmental pollution, and the like, and are being abolished on an international level.

In recent years, the use of an improved water-based cleaning agent or a water-rinsable cleaning agent has been studied to remove dirt mainly composed of organic substances such as oils and fats present on solid surfaces of precision parts and jigs. ing. These detergents have a detergency equal to or higher than that of a solvent-based detergent by appropriately selecting and blending a surfactant or a builder used for the detergent,
Alternatively, it has various advantages such as low risk of fire and explosion. In recent years, in consideration of the rusting properties and electrical properties of precision parts and jigs when cleaning agents remain, inorganic alkalis such as alkali metals such as sodium and potassium and alkaline earth metals such as calcium are used. Rather, organic alkalis, that is, amine-based compounds are blended, and especially difficult-to-clean contaminants such as animal and vegetable oils, ester-based oils and waxes, rosin-based fluxes and waxes, and highly polar water-insoluble polymer substances. There has been proposed a detergent having improved detergency.

For example, JP-A-59-134891 discloses the use of alcohol ether solvents and water-soluble amines and / or amides. Japanese Patent Publication No. 5-1840 discloses a specific alkylamine and a high boiling point solvent. JP-A-5-295392 discloses that a glycol-based solvent, amines and / or a surfactant and, if necessary, water can be used. The use of glycols or glycols and primary or secondary amines is indicated.

However, since the amount of the amine compound used in these techniques in a detergent is very large,
The pH of the cleaning agent itself becomes high, causing corrosion of metals such as aluminum, nickel, copper, zinc, and tin, alloys such as brass, brass, and solder, and plated components.

Japanese Patent Application Laid-Open No. 4-57897 discloses a polyoxyalkylene adduct of an alcohol, a fatty acid and an alkylamine, which has 1 to 5 nitrogen atoms and a molecular weight of 50 to 3.
Japanese Patent Application Laid-Open No. 4-57898 discloses the use of an amine compound and a polyoxyalkylene adduct of an alcohol, a fatty acid and an alkylamine, water, a surfactant and a nitrogen atom having 1 to 5 nitrogen atoms. Having a molecular weight of 50 to 30
And the pH of the detergent is 6.5 to 6.5 using an amine compound
JP-A-4-88098 discloses that a saturated monohydric alcohol having 1 to 3 carbon atoms and HLB5 can be used.
The use of polyoxyethylene alkyl ether type nonionic surfactants of Nos. 8 to 8 and a specific amine is disclosed in
Japanese Patent Application Laid-Open No. 73576/1995 discloses that a higher alcohol-based polyoxyphenyl ether and an organic amine-based monoethanolamine or triethanolamine are used.
Is adjusted to 6 to 9 to use a mixed solution.

However, the amine compounds used in these techniques are used by limiting the amount added to the detergent or the pH of the detergent in order to reduce the influence on members. In particular, the cleaning properties of the difficult-to-clean contaminants are insufficient.

On the other hand, JP-A-4-110399 discloses that tetrahydrofurfuryl alcohol or an alkylene oxide adduct thereof, a nonionic surfactant and an amine compound are used. It is possible to use glycols or glycol ethers, a nonionic surfactant and a specific amine compound, and JP-A-4-142399 discloses that alcohols, a nonionic surfactant and a specific amine compound are used. Japanese Patent Application Laid-Open No. 5-25494 discloses that a compound based on 1 to 6 mol of ethylene oxide of cyclohexylamine is used as an essential component.
Japanese Patent Application Laid-Open Publication No. H11-163873 discloses using an alkylene oxide adduct of an aliphatic alcohol having 6 to 22 carbon atoms and an amine compound having a cyclohexane ring.

However, the amine-based compounds used in these techniques have terminal active hydrogen added with ethylene oxide, and thus have reduced alkali activity. For this reason, in particular, the cleanability of the difficult-to-clean contaminants is insufficient.

As described above, when precision parts, jigs and the like are cleaned by using a conventional cleaning agent containing an amine compound, particularly, metals such as aluminum, nickel, copper, zinc, tin, and brass are used. , Alloys such as brass and solder, and parts plated with metals having different ionization tendencies are corroded, and the cleaning properties of the above-mentioned hard-to-clean contaminants are insufficient.

It should be noted that, among alkali cleaning agents containing an alkali metal, as a cleaning agent for preventing corrosion of copper, zinc, tin, etc., for example, Japanese Patent Application Laid-Open No. 5-43897 discloses a nonionic surfactant or a nonionic surfactant. Anionic surfactants and alkali metal silicates, hydroxides, carbonates or bicarbonates, acrylic acid, methacrylic acid or salts thereof and methacrylsulfonic acid, vinylsulfonic acid, allylsulfonic acid as constituent units , And the weight average is 1,000-10,000
It has been shown to use a copolymer that is But,
There are problems such as deterioration of electrical characteristics of electronic components when the cleaning agent remains, rust generation of precision components and jigs and tools, and poor rinsing properties due to the inclusion of high molecular substances.

An object of the present invention is to solve a problem which has not been solved thus far. That is,
Improves the shortcomings of conventional water-based cleaning agents, and includes precision materials including metals such as aluminum, nickel, copper, zinc, and tin, alloys such as brass, brass, and solder, and materials that are easily corroded, such as plated parts. Oils and fats, machine oils, cutting oils, which exist on the solid surface of parts or jigs and tools used in the assembly process
Water-based cleaning that excels in removing dirt such as grease, liquid crystal, and rosin flux, and does not corrode metals such as aluminum, nickel, copper, zinc, and tin, alloys such as brass, brass, and solder, and plated components. Agent composition.

[0014]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, aluminum,
Metal parts such as nickel, copper, zinc, tin, etc., alloys such as brass, brass, solder, etc., and precision parts including easily corroded materials such as plated parts or jigs and tools used in the assembling process are water-based. When a composition containing a carbonate of a specific amine compound is used as a cleaning agent when cleaning with a cleaning material, the composition is present on the solid surface of precision parts or jigs and tools used in the assembling process thereof. Excellent in the removal of dirt such as oils and fats, machine oil, cutting oil, grease, liquid crystal, rosin flux, and metals such as aluminum, nickel, copper, zinc, tin, and alloys such as brass, brass, solder, and the like. It has been found that corrosion of plated parts and the like can be prevented, and the present invention has been completed.

That is, the gist of the present invention is as follows: (1) The number of nitrogen atoms is 1 to 5, and the molecular weight is 50 to 50.
Carbonates of amine compounds in the range of 300 (however,
Excluding anidine carbonate), the general formula (1),
(2) and (3)

[0016]

Embedded image

(Wherein, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, R ² and R ³ each represent an alkylene group having 2 to 4 carbon atoms. X represents a hydrogen atom or a C ¹ to C 4 alkyl group). M represents 1 to 7, n represents 0 to 7, and p represents 0.
To 5, q represent an integer of 0 to 5. A composition comprising at least one alkylene oxide compound selected from the group consisting of compounds represented by
An aqueous detergent composition used for cleaning jigs and tools, (2) the content of the carbonate of the amine compound is 0.05 to
70% by weight, and containing an alkylene oxide compound
The amount Ru 5-95% der (1) an aqueous detergent composition according, (3) one or more surfactants further comprising (1) or (2) an aqueous wash according (4) The aqueous cleaning composition according to any one of the above (1) to (3), further comprising a hydrocarbon having 10 to 18 carbon atoms, (5) a water content of 5 to 30% by weight. der Ru (1) Symbol placement aqueous detergent composition, a. Hereinafter, the present invention will be described.

Among the components used in the aqueous detergent composition of the present invention, the amine compound carbonates include amine compounds having 1 to 5 nitrogen atoms and a molecular weight of 50 to 300. Carbonates are used. Here, from the viewpoint of the odor and the rinsing property of the obtained detergent composition, carbonates of amine compounds having 1 or 2 nitrogen atoms and a molecular weight in the range of 100 to 250 are more preferable.

Specific examples of such amine compounds include:
The following substances may be mentioned. (A) monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, methylmonoethanolamine, dimethylmonoethanolamine, methyldiethanolamine, butylmonoethanolamine, dibutylmonoethanolamine, trimethylaminopropylethanolamine, trimethylhydroxyethyldiethylenetriamine Alkanolamines. (B) morpholine, N-methylmorpholine, N-ethylmorpholine, 2,6-dimethylmorpholine, 4- (2-
Hydroxyethyl) morpholine, 4-aminomorpholine, 4- (2-aminoethyl) morpholine, 4- (3-
Morpholines such as aminopropyl) morpholine;

(C) Complexes such as 4-aminomethylpyridine, aminomethylpiperazine, bisaminopropylpiperazine, trimethylaminoethylpiperazine, 2-aminomethylpiperidine, 4-aminomethylpiperidine, 2-methylpyrazine, quinoxaline and methylimidazole Cyclic amines. (D) diaminopropane, diaminohexane, diaminooctane, diaminododecane, diaminodiphenylmethane, diaminodiphenylethane, 4,4-methylenebiscyclohexylamine, 1,3-diaminoxylene,
1,3-bis (aminomethyl) cyclohexane, triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, tetramethylhexamethylenediamine, methyldiaminopropane, dimethyldiaminopropane, dibutyldiaminopropane, stearylpropylenediamine, N-cyclohexyl-1 And diamines such as 1,3-diaminopropane, 1,2-diaminoanthraquinone and pentamethyldiethylenetriamine.

(E) Polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine. (F) Cyclic amines such as cyclohexylamine, aniline, benzylamine, dicyclohexylamine, dibenzylamine and tribenzylamine.

(G) propylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, laurylamine, tridecylamine, myristylamine, pentadecylamine, cetylamine, heptadecylamine, Stearylamine, nonadecylamine, eicosylamine, diethylamine, dibutylamine, dioctylamine, methylhexylamine, tributylamine, trioctylamine, dimethyloctylamine,
Linear alkylamines having a linear alkyl group having 1 to 22 carbon atoms, such as dimethyllaurylamine and dimethylstearylamine.

(H) s-butylamine, isobutylamine, t-butylamine, 1-methylbutylamine,
Ethylpropylamine, 2-methylbutylamine, isoamylamine, dimethylpropylamine, t-amylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane, 3-aminoheptane, 1-methylheptylamine, Branches having a branched alkyl group having 1 to 22 carbon atoms, such as 2-ethylhexylamine, 1,5-dimethylhexylamine, t-octylamine, t-tridecylamine, t-nanodecylamine, diisobutylamine, and diisopropylethylamine. Chain alkylamines and the like.

Of the above compounds, monoethanolamine, diethanolamine, triethanolamine, methyl monoethanolamine, dimethyl monoethanolamine, methyldiethanolamine, butyl monoethanolamine, trimethylaminopropylethanolamine,
Trimethylhydroxyethyldiethylenetriamine;

Morpholine, N-methylmorpholine, N-
Ethyl morpholine, 2,6-dimethyl morpholine, 4-
(2-hydroxyethyl) morpholine, 4-aminomorpholine, 4- (2-aminoethyl) morpholine, 4-
(3-aminopropyl) morpholine, 4-aminomethylpyridine, bisaminopropylpiperazine, 2-aminomethylpiperidine, 4-aminomethylpiperidine;

Diaminopropane, diaminohexane, diaminooctane, diaminododecane, 1,3-diaminoxylene, 1,3-bis (aminomethyl) cyclohexane, tetramethylethylenediamine, tetramethylpropylenediamine, methyldiaminopropane, dimethyldiaminopropane, Dibutyldiaminopropane, stearylpropylenediamine, N-cyclohexyl-1,3-
Diaminopropane, pentamethyldiethylenetriamine; diethylenetriamine, triethylenetetramine,
Tetraethylenepentamine;

Cyclohexylamine, benzylamine,
Dicyclohexylamine; propylamine, butylamine, amylamine, hexylamine, heptylamine,
Octylamine, nonylamine, decylamine, undecylamine, laurylamine, tridecylamine, myristylamine, pentadecylamine, cetylamine, heptadecylamine, stearylamine, nonadecylamine, eicosylamine, diethylamine, dibutylamine, dioctylamine, methylhexyl Amine;

S-butylamine, isobutylamine, t
-Butylamine, 1-methylbutylamine, 1-ethylpropylamine, 2-methylbutylamine, isoamylamine, dimethylpropylamine, t-amylamine,
1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane, 3-aminoheptane,
1-methylheptylamine, 2-ethylhexylamine, 1,5-dimethylhexylamine, t-octylamine, t-tridecylamine, t-nanodecylamine,
Diisobutylamine and diisopropylethylamine can be preferably used from the viewpoints of performance and availability.

The carbonate of the amine compound used in the aqueous detergent composition of the present invention is obtained by neutralizing the above amine compound with carbonic acid, thereby increasing the pH of the detergent when blended in the detergent. Of metal, such as aluminum, nickel, copper, zinc, and tin; alloys such as brass, brass, and solder; and corrosion of plated components and the like.

The carbonate of the amine compound can be obtained by a commonly used known method.
It is obtained by blowing carbon dioxide gas into a solution of the above-mentioned amine compound in water and / or a solvent. The degree of neutralization at this time is determined by measuring the pH of the solution over time and determining when the value becomes constant as an end point. However, it is preferable to suppress the pH of the detergent itself containing the carbonate of the amine compound to 10 or less from the viewpoint of preventing corrosion of metals.

The amount of the carbonate of these amine compounds is not particularly limited. However, from the viewpoint of the effect of detergency and the persistence thereof, 0.05 to 7% in the detergent composition.
0% by weight, particularly preferably 0.1 to 50% by weight is blended.

The water-based detergent composition of the present invention can be used in combination with the alkylene oxide compounds represented by the general formulas (1), (2) and (3) to improve detergency. .

In the general formulas (1), (2) and (3), R ¹
Is required to be a hydrocarbon group having 1 to 8 carbon atoms, but is preferably a hydrocarbon group having 2 to 6 carbon atoms from the viewpoint of solubility in water. If R ¹ is not a hydrocarbon group, the affinity with organic stains such as flux and mineral oil decreases. Also, m is 1 to 7, n is 0 to 7, p is 0 to 5, q
Is required to be an integer of 0 to 5. M + n is in the range of 1 to 14, and p + q is in the range of 0 to 10. However, m + n is in the range of 2 to 4 from the viewpoint of solubility in water and detergency against organic stains. p + q is 0
A range of 4 is preferred.

Specific examples of such alkylene oxide compounds include methanol, ethanol, propanol,
Alcohols having a linear or branched alkyl group such as butanol, isobutanol, hexanol and octanol; phenols such as phenol and cresol; alicyclic alcohols such as cyclohexanol; acetic acid, propionic acid, hexanoic acid, Fatty acids having a linear or branched alkyl group such as isooctylic acid; organic carboxylic acids such as methacrylic acid and benzoic acid; linear acids such as ethylamine, diethylamine, hexylamine, dibutylamine, octylamine, benzylamine and cyclohexylamine;
Examples thereof include those in which an alkylene (ethylene, propylene, butylene) oxide is added alone or in combination with an amine-based compound having a branched chain, an aromatic or alicyclic hydrocarbon group, and the like. Compounds in which terminal hydroxyl groups are methylated, ethylated, or butylated with alkyl chloride or the like, or esterified with acetic acid, propionic acid, or the like. One of the above alkylene oxide compounds may be used alone, or two or more thereof may be used in combination.

Specific examples include the following compounds. Ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, hexaethylene glycol monomethyl ether, heptaethylene glycol monomethyl ether (each of the above compounds (POE) ₁ monomethyl ether , (POE) ₂ monomethyl ether, (POE) ₃
Monomethyl ether, (POE) ₄ monomethyl ether, (POE) ₅ monomethyl ether, (POE) ₆ monomethyl ether, (POE) ₇ monomethyl ether,
May be abbreviated. Also, sometimes referred to as collectively these compounds and (POE) ₁ ~ ₇ monomethyl ether. In addition, similar compounds and the like may be abbreviated as described above with expressions corresponding thereto. ),

[0036] (POE) ₁ ~ ₇ mono ethyl ether,
(POE) ₁ ~ ₇ monopropyl ether, (POE) _1
1-7 monobutyl ether, (POE) _{1 1-7} monoisobutyl ether, (POE) _{1 1-7} monoallyl ether,
(POE) ₁ to ₇ monohexyl ether, (POE) ₁
~ ₇ mono 2-ethylhexyl ether, (POE) ₁ ~
₇ monooctyl ether, (POE) _1-7 monophenyl ether, (POE) ethylene glycol monomethyl ethers such as _1-7 monobenzyl ether.

[0037] (POE) ₁ ~ ₄ dimethyl ether, (P
OE) ₁ ~ ₄ diethyl ether, (POE) ₁ ~ ₄ dipropyl ether, (POE) ₁ ~ ₄ dibutyl ether,
(POE) ₁ ~ ₄ diallyl ether, (POE) ₆ ~ ₇
Dimethyl ether, (POE) ₆ ~ ₇ diethyl ether, (POE) ₆ ~ ₇ dipropyl ether, (POE)
_6-7 dibutyl ether, (POE) _6-7 diallyl ether, diethylene glycol ethyl methyl ether,
Ethylene glycol diethers such as diethylene glycol butyl methyl ether and diethylene glycol 2-ethylhexyl methyl ether.

[0038] (POP) ₁ ~ ₇ monomethyl ether,
((POP) ₁ to ₇ monoethyl ether, (POP) ₁
To ₇ monopropyl ether, (POP) ₁ to ₇ monobutyl ether, (POP) ₁ to ₇ monoallyl ether,
(POP) ₁ to ₇ monohexyl ether, (POP) ₁
~ ₇ mono 2-ethylhexyl ether, (POP) ₁ ~
₇ monooctyl ether, (POP) _1-7 monophenyl ether, (POP) Propylene glycol monomethyl ethers such as _1-7 monobenzyl ether. (PO
P) means (PO) except that ethylene is propylene.
It is the same abbreviation as E).

[0039] (POP) ₁ ~ ₇ dimethyl ether, (P
OP) ₁ ~ ₇ diethyl ether, (POP) ₁ ~ ₇ dipropyl ether, (POP) ₁ ~ ₇ dibutyl ether,
(POP) Propylene glycol diethers such as ₁ to ₇ diallyl ether, dipropylene glycol isopropyl methyl ether and dipropylene glycol isopropyl ethyl ether.

[0040] (POE) ₁ ~ ₇ monomethyl ether acetate, (POE) ₁ ~ ₇ monoethyl ether acetate, (POE) ₁ ~ ₇ monopropyl ether acetate, (POE) ₁ ~ ₇ monobutyl ether acetate,
(POE) ₁ ~ ₇ monoallyl ether acetate, (P
OE) ₁ to ₇ monohexyl ether acetate, (PO
E) ₁ ~ ₇ mono-octyl ether acetate, (PO
E) ₁ ~ ₇ monophenyl ether acetate, (PO
E) ethylene glycol monomethyl ether acetate such as _1-7 monobenzyl ether acetate.

[0041] (POP) ₁ ~ ₇ monomethyl ether acetate, (POP) ₁ ~ ₇ monoethyl ether acetate, (POP) ₁ ~ ₇ monopropyl ether acetate, (POP) ₁ ~ ₇ monobutyl ether acetate,
(POP) ₁ to ₇ monoallyl ether acetate, (P
OP) ₁ to ₇ monohexyl ether acetate, (PO
P) ₁ to ₇ monooctyl ether acetate, (PO
P) ₁ to ₇ monophenyl ether acetate, (PO
P) Propylene glycol monoether acetates such as ₁ to ₇ monobenzyl ether acetate.

Monopropylene glycol diacetates such as propylene glycol diacetate. Alcohols having a straight-chain or branched-chain alkyl group as a raw material of the hydrocarbon group, compounds obtained by blocking and randomly adding ethylene oxide and propylene oxide to alicyclic alcohols, (POE) ₁ to ₇ (POP) ₁ to _{7
Monoethers; (POE) 1 ~ 7 (} POP) 1 ~ 7 diethers.

The raw material of the above-mentioned hydrocarbon group is linear or branched.
Alcohols with branched alkyl groups, alicyclic alcohols
Acetic acid, propionic acid, hexanoic acid,
Has a linear or branched alkyl group such as isooctylic acid
Fatty acids, organic carboxylic acids such as methacrylic acid and benzoic acid
Compound using For example, (POE)_One~₇Monomethyl
Esters, (POE)_One~₇Monoethyl ester, meta
Crylic acid (POE) _One~₇The adduct, benzoic acid (PO
E)_One~₇Glycol monoesters such as adducts; (P
OE)_One~₇Dimethyl ester, (POE)_One~₇Jie
Glycol diesters such as tyl ester;

Instead of alcohols having a linear or branched alkyl group and alicyclic alcohols, which are raw materials for the hydrocarbon groups, ethylamine, diethylamine, hexylamine, dibutylamine, octylamine, benzylamine, Straight-chain, branched-chain such as cyclohexylamine,
A compound using an amine or the like having an aromatic or alicyclic hydrocarbon group. For example, (POE) ₁ ~ ₇ ethylamine,
(POE) ₁ ~ ₇ diethylamine, (POE) ₁ ~ ₇ hexylamine, (POE) ₁ ~ ₇ dibutylamine, (P
Glycol monoamines such as OE) ₁ to ₇ octylamine, (POE) ₁ to ₇ benzylamine, and (POE) ₁ to ₇ cyclohexylamine.

Of the above compounds, those listed below are preferably used from the viewpoint of performance and availability.
(POE) ₁ to ₅ monomethyl ether, (POE) ₁ to
₅ monoethyl ether, (POE) ₁ ~ ₅ monopropyl ether, (POE) ₁ ~ ₅ monobutyl ether, (P
OE) ₁ ~ ₂ monoisobutyl ether, (POE) ₁ ~
₂ monoallyl ether, (POE) ₁ ~ ₂ monohexyl ether, (POE) ₁ ~ ₂ mono-2-ethylhexyl ether, (POE) ₁ ~ ₅ monophenyl ether, (P
OE) ₁ ~ ₅ monobenzyl ether;

Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, diethylene glycol 2-ethylhexyl methyl ether;
Triethylene glycol dimethyl ether; tetraethylene glycol dimethyl ether;

[0047] (POP) ₁ ~ ₃ monomethyl ether,
(POP) ₁ ~ ₃ monoethyl ether, (POP) ₁ ~
₃ monopropyl ether, (POP) ₁ ~ ₃ monobutyl ether, (POP) ₁ ~ ₃ monophenyl ether,
(POP) ₁ ~ ₃ monobenzyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene Glycol isopropyl methyl ether, dipropylene glycol isopropyl ethyl ether; tripropylene glycol dimethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate;

These alkylene oxide compounds are
For example, an alcohol having a hydrocarbon group having 1 to 8 carbon atoms,
Phenols, fatty acids, organic carboxylic acids, and amine compounds have 2 carbon atoms under heating in the presence of a catalyst such as caustic soda.
To 4 alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) in liquid or gaseous form and reacted. Further, those obtained by alkylating the terminal hydroxyl groups of these alkylene oxide adducts with an alkyl chloride or the like or esterifying them with an organic acid or the like can be used.

When the alkylene oxide is added, random addition polymerization in which two or more alkylene oxides are mixed and reacted or block addition polymerization in which the alkylene oxides are sequentially added may be performed.

These alkylene oxide compounds are:
It is preferable to add 5 to 95% by weight, especially 10 to 70% by weight in the detergent composition. If the amount is less than this range, the effect of adding the alkylene oxide compound to the detergency and its sustainability tends to be insufficient.
In addition, if the content exceeds this range, there is a danger of flammability.

The water-based detergent composition of the present invention further increases the detergency by adding a surfactant. As the surfactant, any of anionic, cationic, nonionic and amphoteric surfactants can be used.

More specifically, fatty acid salts, higher alcohol sulfate salts, liquid fatty oil sulfate salts,
Anions such as sulfates of aliphatic amines and aliphatic amides, phosphate salts of fatty alcohols, sulfonates of dibasic fatty acid esters, fatty acid amide sulfonates, alkylallyl sulfonates, and naphthalene sulfonates of formalin condensation Cationic activators such as aliphatic amine salts, quaternary ammonium salts, and alkylpyridinium salts; polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenol ethers, polyoxyalkylene alkyl amines, and polyoxyalkylene alkyl Nonionic activators such as esters, sorbitan alkyl esters and polyoxysorbitan alkyl esters; or zwitterions such as alkyl betaines, alkyl dimethylamine oxides and alkyl alanines Active agent and the like as those were the main. Here, polyoxyalkylene refers to a polymer of ethylene oxide, propylene oxide or butylene oxide. Among these surfactants,
In particular, nonionic surfactants having an average HLB of 4 to 18 exhibit excellent effects.

Specifically, (POE) ₁ to ₄₀ octyl ether, monomeric to _40- mer ethylene oxide and ether of a synthetic alcohol having 12 to 14 carbon atoms ((PO
E) abbreviated as ₁ ~ ₄₀ C ₁₂ ~ ₁₄ Synthesis alcohol ether. ), (POE) ₁ ~ ₄₇ lauryl ether, (PO
E) ₂ to ₂₀ cetyl ether, (POE) ₂ to ₃₀ stearyl ether, (POE) ₂ to ₃₅ oleyl ether, (P
OE) ₂ to ₄₀ octyl phenyl ether, (POE) ₂
Polyoxyethylene alkyl ethers such as _-45 nonylphenyl ether;

Sorbitan monolauryl ester, sorbitan monopalmityl ester, sorbitan monostearyl ester, sorbitan monooleyl ester, etc .; sorbitan monoalkyl esters; (POE) ₁ to ₂₅ sorbitan monolauryl ester, (POE) ₁ to ₂₅ sorbitan mono palmityl ester, (POE) _1-30 sorbitan monostearyl ester, (POE) polyoxyethylene sorbitan alkyl esters such as ₁ to ₃₀ sorbitan mono-oleyl ester; (POE) ₁₀ ~ ₄₀ sorbitan tristearate Lil ester, (POE) Examples thereof include polyoxyethylene sorbitan trialkyl esters such as ₁₀ to ₄₀ sorbitan trioleyl ester.

Of the above compounds, (POE) ₅ to ₉ C
_12-14 synthetic alcohol ether, (POE) ₄ ~ ₁₀ lauryl ether, (POE) ₅ ~ ₈ cetyl ether, (P
OE) ₁₀ to ₁₅ stearyl ether, (POE) ₅ to ₁₅ oleyl ether, (POE) ₆ to ₁₀ octyl phenyl ether, (POE) ₅ to ₁₃ nonyl phenyl ether, sorbitan monolauryl ester, sorbitan monopalmityl ester, sorbitan mono stearyl ester, sorbitan mono-oleyl ester, (POE) ₅ ~ ₂₀ sorbitan monolauryl ester, (POE) ₅ ~ ₂₀ sorbitan palmityl ester, (POE) ₅ ~ ₂₀ sorbitan monostearyl ester, (POE) ₅ ~ ₂₀ sorbitan oleyl ester, (POE) ₁₅ ~ ₃₀ sorbitan tristearate Lil ester, (POE) ₁₅ ~ ₃₀ sorbitan trioleyl esters detergency against stains organic, and preferably used from the viewpoint of rinsing properties.

The amount of these surfactants is not particularly limited, but is preferably 0.5 to 35% by weight in the aqueous detergent composition of the present invention in order to obtain the effect of adding the surfactant.
Particularly, it is preferable to add 3 to 30% by weight.

The water-based detergent composition of the present invention further increases the detergency of dirt having a small polarity by adding a hydrocarbon.

Such hydrocarbons include those having 10 to 1 carbon atoms.
8, straight-chain or branched-chain saturated or unsaturated hydrocarbons such as decane, dodecane, tetradecane, hexadecane, octadecane, decene, dodecene, tetradecene, hexadecene, octadecene; nonylbenzene, dodecyl Alkylbenzenes such as benzene; naphthalene compounds such as methylnaphthalene and dimethylnaphthalene; and cyclo compounds such as cyclodecane and cyclododecene. Of these, straight or branched chain saturated or unsaturated hydrocarbons having 12 to 18 carbon atoms are preferable, and olefin hydrocarbons are particularly preferable in consideration of detergency, handling, and the like.

These hydrocarbons are used in the aqueous detergent composition of the present invention in view of detergency against low (non) polar stains.
It is preferred that the compounding amount be from 80 to 80% by weight, especially from 20 to 70% by weight.

The detergent composition of the present invention may contain water as appropriate from the viewpoints of safety and workability. Water is preferably incorporated in the detergent composition in an amount of 5 to 30%.

The detergent composition of the present invention may contain other additives such as hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid and the like which are usually used in detergents as long as their effects are not impaired. Compounds having organic or inorganic chelating power such as aminocarboxylates, preservatives, rust preventives, defoamers such as silicon, amine and phenolic antioxidants, coconut fatty acid methyl and benzyl acetate Ester, amine-based additives, alcohols and the like can be appropriately used in combination.

The cleaning composition of the present invention can be produced by mixing the above-mentioned components and optional components in a conventional manner.

To clean a glass containing a modified oxide composed of metal ions using the cleaning composition of the present invention, and to clean electronic parts and precision parts for electric, electronic, optical and precision industries using the same, For example, using the cleaning composition of the present invention, immersion method, ultrasonic cleaning method, immersion rocking method, spray method,
Various washing methods such as a hand wiping method can be adopted, and a method of continuously performing a method such as rinsing with a solvent or hot water at the end,
It is cited as an efficient cleaning method, and favorable results can be obtained.

[0065]

EXAMPLES The present invention will be described in detail below with reference to Production Examples, Production Comparative Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. Production Example 1 In a 500 ml glass four-necked flask, 50.0 g of diethanolamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
(0.48 mol) and 50.0 g of water were added, and carbon dioxide (gas) was blown from the cylinder at a flow rate of 200 ml / min while stirring at 30 ° C. After 3.5 hours, the pH of the solution
Became constant at 8.3, the neutralization was terminated. From this, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain 61.1 g of diethanolamine carbonate.

Production Example 2 50.0 g of triethanolamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 500 ml glass four-necked flask.
(0.34 mol), water 25.0 g, ethanol 25.0
g and stirring at 30 ° C.
Carbon dioxide (gas) was blown in at a flow rate of ml / min.
After 4.5 hours, neutralization was terminated when the pH of the solution became constant at 8.3. From this, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain 54.1 g of carbonate of triethanolamine.

Production Example 3 N-methyldiethanolamine (reagent, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was placed in a 500 ml four-neck glass flask.
0.0 g (0.42 mol) and 50.0 g of water
Carbon dioxide (gas) was blown from the cylinder at a flow rate of 200 ml / min while stirring at ℃. After 4.5 hours, neutralization was terminated when the pH of the solution became constant at 8.9. From this, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain 62.6 g of N-methyldiethanolamine carbonate.

Production Example 4 50.0 g of N-methylmorpholine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 500 ml glass four-necked flask.
(0.49 mol) and 50.0 g of water were added, and carbon dioxide (gas) was blown from the cylinder at a flow rate of 200 ml / min while stirring at 30 ° C. After 4.0 hours, the pH of the solution
Became constant at 8.5, the neutralization was terminated. From this, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain 56.7 g of N-methylmorpholine carbonate.

Production Example 5 In a 500 ml four-neck glass flask, 50.0 g (0.32 mol) of N-cyclohexyl-1,3-diaminopropane (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 25.25 g of water were added. 0
g and 25.0 g of ethanol, and carbon dioxide (gas) was blown from the cylinder at a flow rate of 200 ml / min while stirring at 30 ° C. After 4.5 hours, neutralization was terminated when the pH of the solution became constant at 8.9. From this, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain 58.8 g of N-cyclohexyl-1,3-diaminopropane carbonate.

Production Example 6 50.0 g of n-octylamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 500 ml four-neck glass flask.
(0.39 mol) and 50.0 g of water were added, and carbon dioxide (gas) was blown from the cylinder at a flow rate of 200 ml / min while stirring at 30 ° C. After 3.5 hours, the pH of the solution
Was constant at 8.8, neutralization was terminated. From this, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain 49.3 g of carbonate of n-octylamine.

Production Comparative Example 1 N-methyldiethanolamine (reagent, Tokyo Chemical Industry Co., Ltd.) 5 was placed in a 500 ml glass three-necked flask.
0.0 g (0.42 mol) and 50.0 g of water
While stirring at 37 ° C., 36% hydrochloric acid (reagent, manufactured by Katayama Chemical Industry Co., Ltd.) diluted with water to 10% (w / w) was added to 1%.
53.1 g (0.42 mol) was added dropwise. From this,
The solvent was distilled off under reduced pressure using a rotary evaporator, and 5
1.8 g of N-methyldiethanolamine hydrochloride were obtained.

Comparative Production Example 2 50.0 g of N-methylmorpholine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 500 ml three-neck glass flask.
(0.43 mol) and water (50.0 g) were added, and while stirring at 30 ° C., sulfuric acid (reagent, manufactured by Katayama Chemical Industry Co., Ltd.) was diluted to 10% (w / w) with water to obtain 213. 0.0g
(0.22 mol) was added dropwise. From this, the solvent was distilled off under reduced pressure using a rotary evaporator, and 57.0 g of N
-The sulfate of methylmorpholine was obtained.

Production Comparative Example 3 50.0 g (0.32 mol) of N-cyclohexyl-1,3-diaminopropane (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) and 50.000 g of water were placed in a 500 ml three-neck glass flask. 0
g, and acetic acid (reagent, manufactured by Katayama Chemical Industry Co., Ltd.) diluted to 10% (w / w) with water was added dropwise to 384.3 g (0.64 mol) while stirring at 30 ° C. . From this, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain 53.7 g of N-cyclohexyl-1,3-diaminopropane acetate.

Comparative Production Example 4 In a 500 ml three-neck glass flask, 50.0 g of n-octylamine (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) was used.
(0.39 mol) and 50.0 g of water, and 153.0 g (0. 0) of a 50% (w / w) aqueous solution of gluconic acid (reagent, manufactured by Katayama Chemical Industry Co., Ltd.) while stirring at 30 ° C. 39
Mol) was added dropwise. From this, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain 75.6 g of gluconate of n-octylamine.

Examples 1 to 10 and Comparative Examples 1 to 8 Cleaning tests were carried out by washing with an aqueous detergent composition comprising the components shown in Tables 1 and 2. Table 3 shows the results. Table 4 shows the origin of the compounds shown in Tables 1 and 2. The test conditions are as follows.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

(1) Detergency test (Preparation of test piece) Aluminum (JIS H4000) of 20 mm × 50 mm × 2 mm and solder (J
IS Z3282 (30SNA)) test piece (Taiyu Kiki Co., Ltd.) and flux (SOLDERITE Y-2)
0, manufactured by Tamura Seisakusho Co., Ltd.) at a rate of 2.5 g / m ² . After reflowing at 270 ° C. for 2 minutes, the sample was cooled to room temperature and used as a test piece for flux. Furthermore, copper of 20 mm × 50 mm × 2 mm (JIS H31
A mineral oil-based press working lubricating oil (Unipres PA5, manufactured by Nippon Oil Co., Ltd.) was applied at a rate of 0.5 g / m ^{2 to} a test piece (manufactured by Taiyu Kikai Co., Ltd.) at a rate of 0.5 g / m ^2. A test piece for press oil was used.

(Cleaning test) The above test piece was heated at 60 ° C.
Immersed in the aqueous cleaning composition shown in Tables 1 and 2
9 kHz, 200 W ultrasonic cleaning equipment (SILENTSONIC UT
-204, manufactured by Sharp Corporation) for 5 minutes. Then
It was immersed in ion-exchanged water at 30 ° C., and rinsed for 1 minute with the same ultrasonic cleaner as used for cleaning. Further, a final rinse was performed with flowing deionized water for 1 minute. Then, after air blowing for 1 minute, it was dried at 80 ° C. for 10 minutes by a blower constant temperature dryer (FV-630, manufactured by Toyo Seisakusho).

(Evaluation Method and Evaluation Criteria) Evaluation of the detergency of the flux and the press oil was carried out visually at a magnification of 50 times with an optical microscope according to the following criteria. ：: Very clean and very good with no residual flux and press oil on the surface. ○: Almost no residual flux and press oil on the surface.
Good Δ: Slight residual flux and press oil on the surface, slightly poor ×: Poor flux and press oil on the surface, poor

(2) Influence test on members 20 mm × 50 mm × 2 mm aluminum (JIS
H4000), solder (JIS Z3282 (30SN)
A)) and a test piece (manufactured by Taiyu Kiki Co., Ltd.) made of copper (JIS H3100) were immersed in a stock solution of a water-based detergent composition described in Tables 1 and 2 and a 5% (w / w) aqueous solution, and then at 60 ° C. Held. The surface state of the test piece after 2 hours and 24 hours was visually observed.

(Evaluation Criteria) 良好: Very good, unchanged from before immersion. ：: The surface is flat and good, although the gloss is slightly reduced. ：: No gloss, discolored, slightly poor ×: Badly discolored, rusted, corroded and roughened, bad

As shown in Table 3, the aqueous cleaning composition of the present invention
It was found that it was an excellent detergent composition which exhibited good detergency in any of aluminum, solder and copper and did not affect members (Examples 1 to 10). on the other hand,
Compound containing amine compound instead of carbonate (Comparative Example 1)
To 4), even if the salt is not a carbonate (Comparative Example 5)
8) was found to have an adverse effect on the members, although some examples had good cleaning properties.

[0086]

EFFECT OF THE INVENTION By using the aqueous detergent composition of the present invention, metals, alloys, plated parts, etc., which are easily corroded, are contained in precision parts or jigs and tools used in the assembling process thereof. Oils and fats, machine oils, cutting oils, greases, liquid crystals, which are present on those solid surfaces without corroding
Dirt such as rosin-based flux can be removed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C11D 3:30 C11D 3:30 3:20) 3:20) (C11D 3/60 (C11D 3/60 3:30 3:30) 3:20 3:20 3:18) 3:18) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 7/00 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A carbonate of an amine compound having 1 to 5 nitrogen atoms and a molecular weight of 50 to 300 (provided that the carbonate is
Excluding guanidine carbonate) and the general formula
(1), (2) and (3) (Wherein, R ¹ represents a hydrocarbon group having 1 to 8 carbon atoms, R ² and
R ³ represents an alkylene group having 2 to 4 carbon atoms. X
Is a hydrogen atom or an alkyl or acyl group having 1 to 4 carbon atoms
Is shown. m is 1 to 7, n is 0 to 7, p is 0 to 5, and q is 0.
Represents an integer of from 5 to 5. From the group consisting of the compounds represented by
One or more selected alkylene oxide compounds.
A composition comprising: for precision parts or tools
Aqueous detergent compositions that are used in cleaning. 2. An amine compound having a carbonate content of 0.
0.5 to 70% by weight, and an alkylene oxide compound
Aqueous detergent composition content according to claim 1, wherein Ru 5-95% der in. 3. The aqueous detergent composition according to claim 1, further comprising one or more surfactants. 4. The aqueous cleaning composition according to claim 1, further comprising a hydrocarbon having 10 to 18 carbon atoms. 5. A method according to claim 1 moisture content Ru 5-30 wt% der
Serial mounting of the aqueous detergent composition.