JPH07179893A - Cleaning composition - Google Patents

Abstract

PURPOSE:To obtain a stabilized cleaning composition which can inhibit discoloration and corrosion of a metal by using N-methyl-2-pyrrolidone (NMP) or an NMP/water mixed solvent as a cleaning agent. CONSTITUTION:This cleaning composition comprises N-methyl-2-pyrrolidone containing 0 to 30wt% of water and at least one compound selected from phosphine, phenol, imidazolidone, imidazole, and fluorene compounds.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning composition comprising N-methyl-2-pyrrolidone (hereinafter referred to as "NMP") and water, and more specifically, stabilization of NMP and corrosion of metallic materials. It relates to a cleaning composition having a protective effect.

[0002]

NMP is a solvent with low toxicity and excellent biodegradability, and is widely used as a solvent for polymerization, a solvent for paints, and a cleaning agent for pipes of chemical plants. Also recently
It is also used for flux cleaning of electronic materials and deburring of sealants.

However, from the chemical aspect, NM
P is a stable compound under normal use conditions, but it is observed that the metal surface is discolored or corroded when it is in contact with a metal material such as copper or iron at a high temperature for a long time. It is recognized that oxygen is oxidized to generate peroxide and the pH is lowered.

NMP is heated in air at a high temperature (50 to 150).
When used as a cleaning agent at (° C.), NMP peroxide is generated, and as a method for preventing this, a method of contacting metallic copper in a storage state (Patent 5-435)
42), a method of adding a specific amount (5% by weight or more) of water to NMP (Patent No. 5-32623) and the like have been proposed. However, the former is good when stored alone with NMP but not effective against non-flammable NMP / water mixed solvent, and the latter is still NMP or NMP / water mixed when used as a cleaning agent at high temperature for a long time. Deterioration tendency of the solvent is recognized and not always satisfactory.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to NMP and NMP.
Provided is a stabilized cleaning composition capable of suppressing discoloration or corrosion of a metal when a water / water mixed solvent is used as a cleaning agent.

[0006]

[Means for Solving the Problems] As a result of various investigations by the present inventors to solve the above problems, NMP or N
The present inventors have found that the combination of an additive with an MP / water mixed solvent can suppress corrosion of a metal by NMP or an NMP / water mixed solvent, and have reached the present invention.

That is, the present invention comprises N-methyl-2-pyrrolidone containing 0 to 30% by weight of water and one or more compounds selected from phosphines, phenols, imidazolidones, imidazoles or fluorenes. More preferably, it is selected from 100 parts by weight of N-methyl-2-pyrrolidone containing 0 to 30% by weight of water and a compound of phosphines, phenols, imidazolidones, imidazoles or fluorenes. A cleaning composition comprising 0.1 to 5 parts by weight of one or more compounds.

The cleaning composition of the present invention contains, in addition to NMP and water, one or more compounds selected from the compounds of phenols, phosphates, imidazolidones, imidazoles or fluorenes as an additive. On the other hand, water is not always necessary and may absorb water during use, but the effect of the present invention does not change even in such a state as long as it has the above composition range.

The additives in the present invention include, as phosphines, for example, triphenylphosphine oxide,
Examples thereof include triphenylphosphine, phosphine, tricyclohexylphosphine, tri-n-butylphosphine and the like, among which triphenylphosphine oxide and triphenylphosphine are preferable. Examples of the phenols include bisphenol A and bisphenol A-A
F, 2,2-methylenebis (4-ethyl-6-t-butylphenol), 4,4-thiobis (3-methyl-6-)
t-butylphenol), 4,4-butylidene bis (3
-Methyl-6-t-butylphenol), 2,6-di-
Examples thereof include t-butylphenol, 2,6-di-t-butylethylphenol, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, and bisphenol A is preferable. Examples of the imidazolidones include 1,3-dimethyl-2-imidazolidone and 1,3-dimethyl-2-imidazolidinone, of which 1,3-dimethyl-2-imidazolidone is preferable. Examples of the imidazoles include 2-ethyl-4-ethylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-methylimidazole, 1- (cyanoethylaminoethyl) -2-methyl. Imidazole, N-
[2- (2-methyl-1-imidazolyl) ethyl] urea, 1-cyanoethyl-2-undecylimidazole,
1-cyanoethyl-2-methylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 1-cyanoethyl-2-ethyl-4-methylimidazole trimellitate, 1-cyanoethyl-
2-undecyl imidazole trimellitate, 2,4-
Diamino-6 [2-methyl-1-imidazolyl] -ethyl-1,3,5-triazine, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 1-benzyl-2-methyl imidazole, 2-phenyl-4-methyl imidazole, 1-cyanoethyl-2-methyl imidazole, 1-cyanoethyl-2-phenyl imidazole,
2,4-Diamino-6 (2-undecyl-1-imidazolylethyl) -1,3,5-triazine, 2-alkyl-5-formylimidazole, 2,4-dialkyl-
5-formyl imidazole and the like, of which 1,3-dimethyl-2-imidazolidone, 2-ethyl-
4-ethylimidazole is preferred. Examples of fluorenes include fluorene, fluorenyl, fluorenylidene, fluorenylamine, fluorer, fluorenone, fluorenone oxime, and fluorene alcohol, and among them, fluorene is preferable. These additives may be used as a single component, or may be used in combination of two or more kinds.

The additive of the present invention is NMP or NMP /
0.001 to 10 parts by weight with respect to the water mixed solvent,
0.1 to 8 parts by weight is preferable, and 0.1 to 5 parts by weight is more preferable. If it is 0.001 part by weight or less, the effect of preventing metal corrosion is not exhibited, and if it is used in an amount of 10 parts by weight or more, there is no particular effect and it is not necessary.

Depending on the purpose, it may be mixed with other various solvents and the like as long as the effects of the present invention are not impaired.
The various solvents are not particularly limited as long as they are organic compounds that are liquid at room temperature, but usually, paints, washing,
Practically preferred are those used in the fields of oil and fat extraction, spraying aids, inks, etc. Hydrocarbons, alcohols, ethers, chlorinated hydrocarbons, esters, glycols, fluorinated chlorinated hydrocarbons Examples thereof include organic compounds belonging to fluorinated hydrocarbons and perfluoro compounds. Examples of such solvents include heptane, isooctane, cyclohexane, methanol, ethanol,
Isopropanol, n-butyl alcohol, isobutyl alcohol, secondary butyl alcohol, tertiary butyl alcohol, isoamyl alcohol, 2-ethylhexanol, cyclohexanol, n-butyl ether, dioxane, acetone, methyl ethyl ketone, isobutyl ketone, diisobutyl ketone, cyclohexanone, methyl Cyclohexanone, isophorone, methylene chloride, chloroform, 1,2-dichloroethane, trichloroethylene,
Tetrachloroethylene, dichloropropane, methyl formate, ethyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, butyl acetate, amyl acetate, isoamyl acetate, 2-ethylcyclohexyl acetate, ethyl propionate, Butyl propionate, butyl butyrate, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Diethylene glycol dimethyl ether, triethylene glycol, glycerol, 1
-Dodecyl-2-pyrrolidone, 2-pyrrolidone, perfluorohexane, perfluoropentane, perfluorooctane, perfluoroheptane and the like can be mentioned without limitation.

Further, the mixed detergent of the present invention may be mixed with a surfactant and other additives which impart various functions. As the surfactant, any of anionic, cationic, nonionic and amphoteric surfactants can be used. As the additive, in addition to the above various solvents, for example, nitromethane, nitroethane, nitroethane, nitropropane, epichlorohydrin, α-methylstyrene, 2-methyl-2-butene, amylene, 1,2
-Butylene oxide, 3-methyl-1-butyn-3-one, 1,2-butanediol, morpholine, 2,6-t
-Butyl-p-cresol, 1,2,3-benzotriazole and the like can be mentioned.

The method of using the cleaning agent of the present invention is not particularly limited, and various methods such as immersion cleaning, ultrasonic cleaning, hand-wiping cleaning, etc., which are usually carried out, can be exemplified. The use temperature is not particularly limited, but it is preferably used at the boiling point of the cleaning composition or lower.

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

[0015]

【Example】

Examples 1 to 6 A glass vial (100 mL) containing 50 g of NMP / water (85/15) mixed solvent and 1.5 g of the compound shown in Table 1 as an additive was immersed in a constant temperature water bath and kept at 70 ° C. After air bubbling for 15 minutes through dry air in the state, an iron test piece (40 × 20 × 2 mm) was introduced and immersed. Then, the container was sealed and left to stand in a thermostatic dryer kept at 90 ° C. for 2 days, and then changes in pH of the mixed solvent and changes in metal corrosion state were observed. The results are shown in Table 1.

The pH of NMP was found to decrease with the passage of time, but the cause is not clear, but the peroxide generated by the reaction with oxygen in the air is further decomposed to generate an organic acid. Because it is thought that it was done, p
It was speculated that the decrease in H would be an index of the degree of NMP degradation.

Further, when the detergency test was carried out as follows, all the detersive compositions had good oil removal rates of 95% or more. [Cleaning Test] A 100-mesh stainless steel wire mesh (5 cm × 2 cm) weighed was dipped in marquenching oil for quenching, immediately taken out and allowed to stand at room temperature for 2 hours. After weighing the wire mesh with oil, it was immersed in a 200 cc beaker containing 100 g of cleaning solution installed in a constant temperature ultrasonic cleaner kept at 70 ° C., and immediately ultrasonically cleaned for 3 minutes with shaking. After rinsing with warm water of 70 ° C. for 1 minute and drying at 60 ° C. for 1 hour, the weight was measured. Here, the oil removal rate (%) = 100 × (weight of oil attached to wire mesh before washing−weight of oil attached to wire mesh after washing) / (weight of oil attached to wire mesh before washing).

[0018]

[Table 1]

Examples 7 to 12 Copper test pieces (40 × 2) were used instead of the iron test pieces.
Corrosion tests similar to those in Examples 1 to 6 were performed, except that 0 × 2 mm) was used and the additives shown in Table 2 were used. The results are shown in Table 2.

Further, when the detergency test was conducted in the same manner as in Examples 1 to 6, the degreasing rate of any of the detersive compositions was 95.
%, Which was good.

[0021]

[Table 2]

Comparative Examples 1 to 4 The same procedure as in Examples 1 to 6 or 7 to 12 was carried out without adding any additives. At this time, the composition of the cleaning composition and the metal follow the description of each table. The results are shown in Tables 1, 2, and 3.

Further, when the detergency test was conducted in the same manner as in Examples 1 to 6, the degreasing rate of any of the detersive compositions was 95.
%, Which was good. Examples 13 to 18 The additive was 2-ethyl-4-ethylimidazole,
The cleaning composition was prepared to have the composition shown in Table 3 and the same corrosion test as in Examples 1 to 6 was performed. The results are shown in Table 3.

Further, when the detergency test was conducted in the same manner as in Examples 1 to 6, the degreasing rate of all the detersive compositions was 95.
%, Which was good.

[0025]

[Table 3]

[0026]

From the results shown in Tables 1 to 3, it is clear that the cleaning composition of the present invention is effective in preventing corrosion of metals such as copper and iron and in preventing oxidation of NMP.

Therefore, the cleaning composition of the present invention is a cleaning object made of a wide range of materials in the process of removing oils and fats, cutting oils, fluxes, paint removers, etc. adhering to metal products, automobile parts, precision parts and the like. It has a practically preferable effect that an object can be washed with the same detergent.

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Claims (2)

[Claims] 1. N-methyl-2-containing 0-30% by weight of water.
A cleaning composition comprising pyrrolidone and one or more compounds selected from compounds of phosphines, phenols, imidazolidones, imidazoles and fluorenes. 2. N-methyl-2-containing 0 to 30% by weight of water.
Pyrrolidone 100 parts by weight and one or more compounds selected from compounds of phosphines, phenols, imidazolidones, imidazoles or fluorenes 0.001
A cleaning composition consisting of 10 to 10 parts by weight.