JP3558375B2 - Rinse-free low residue cleaning agent - Google Patents

Description

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【表１】

【００１９】
【表２】

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【発明の効果】
本発明は、塩素系溶剤に匹敵する脱脂力を有し、水リンス不要で用いることのできる、安定な液体状の優れた洗浄剤である。[0001]
[Industrial applications]
The present invention relates to an aqueous cleaning agent used for degreasing cleaning of metals, ceramics, glass, plastics, and the like.
[0002]
[Prior art]
Conventionally, as industrial degreasing detergents for metals, ceramics, glass, plastics, etc., aqueous detergents represented by alkali detergents and solvent detergents represented by 1,1,1-trichloroethane have been used. ing.
[0003]
Alkaline detergents, non-ionic surfactants represented by polyoxyethylene alkyl phenyl ether, surfactants such as anionic surfactants represented by sodium alkylbenzene sulfonate, sodium carbonate, sodium silicate, sodium borate, Alkali salts such as sodium phosphate, sodium hydroxide and potassium hydroxide, sodium tripolyphosphate, chelating agents such as ethylenediaminetetraacetate, nitrilotriacetate, gluconate, benzotriazole, amines, alkanolamines, sodium nitrite Rust preventives and the like are appropriately blended. As described in, for example, "Precision Cleaning Technology" Engineering Book p117-120 by Tsuji Osamu and "Precision Cleaning Technology Manual" New Technology Development Center p50-56 by Tsuji Osamu, articles to be cleaned, metal Various types have been proposed depending on the stain.
[0004]
The degreasing cleaning step using the aqueous cleaning agent usually includes a cleaning step, a rinsing step by water washing, and a drying step by hot air or the like.
On the other hand, chlorinated solvents such as 1,1,1-trichloroethane are excellent in degreasing power and penetrating power, and can be applied to all kinds of degreasing such as cutting oil, drawing oil, and press oil. Used in the field of cleaning precision parts that require
[0005]
The degreasing and cleaning step using a chlorinated solvent such as 1,1,1-trichloroethane usually comprises a cleaning step, a rinsing step with a distillate thereof, and a drying step with its steam. A distillation and condensation system is used.
However, in recent years, environmental problems such as groundwater pollution, air pollution, and ozone layer destruction due to chlorine-based solvents have become prominent. In the industrial world, conventional water-based cleaning agents have been applied as cleaning agents to replace them. I am doing it.
[0006]
[Problems to be solved by the invention]
However, when a conventional water-based cleaning agent is used, a rinsing step by water washing is usually required after the washing step, and there is a problem that a large amount of wastewater is discharged from this step. For this reason, a method that unavoidably eliminates the water rinsing step has been tried, but the components of the cleaning agent remain on the article surface as residues, which become solid foreign matters and stains, cause rusting, discoloration, painting and welding. In addition, there is a problem that the post-process such as adhesion is adversely affected, so that it is possible only in the case of rough cleaning where the cleanliness may be low. Therefore, there is a demand for a water-based cleaning agent which has little residue even when used without water rinsing, hardly causes solid foreign matter and stains, has excellent rust prevention properties, and does not affect post-processes.
[0007]
In addition, in order to increase the degreasing power and the penetrating power, the conventional water-based cleaning agents incorporate a large amount of a nonionic surfactant or increase the pH by increasing the amount of an alkali salt. If used without being used, it is difficult to increase the amount of residue, to turn into solid foreign matter, and to obtain a stable liquid state as a product, further adversely affect non-ferrous metals, and reduce the safety for workers.
[0008]
As a method for obtaining a stable liquid state, for example, there is a method using sodium aromatic carboxylate as shown in JP-B-63-13480. However, p-tert-butylbenzoic acid used as a representative of sodium aromatic carboxylate is used. There is a problem that sodium acid has a bad effect on the kidneys and the liver.
[0009]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the above problem can be solved by combining morpholine, a block polymer, a fatty acid and a dicarboxylic acid, and have completed the present invention.
That is, the present invention relates to at least (1) morpholine 0.1 to 20% by weight.
(2) Polyoxyethylene polyoxypropylene block polymer 0.1 to 10% by weight
(3) aliphatic acid having 6 to 12 carbon atoms 0.1 to 20% by weight
(4) 0.1 to 20% by weight of dicarboxylic acid having 6 to 18 carbon atoms
(5) A cleaning agent comprising water and having a pH of 7 to 9.5.
[0010]
If the amount of morpholine is less than 0.1% by weight, the rust-preventive effect on iron decreases. If the amount is more than 20% by weight, corrosion to non-ferrous metals, especially aluminum, an increase in the amount of residues when water rinsing is not performed, and an increase in paint, etc. It is not preferable because of adverse effects.
As the polyoxyethylene polyoxypropylene block polymer, those having an average molecular weight of the polyoxypropylene portion of 600 to 2,000 and an ethylene oxide ratio of 10 to 40% by weight are suitably used. If the amount is less than 0.1% by weight, the detergency is reduced. If the amount is more than 10% by weight, the amount of residue is increased when water rinsing is not performed, and undesirably adversely affects painting and the like.
[0011]
The fatty acid having 6 to 12 carbon atoms is a component necessary for keeping the cleaning agent of the present invention in a stable liquid state in a wide temperature range from a low temperature of normal temperature or lower to a high temperature of 50 ° C. or higher. Straight-chain fatty acids such as acids, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, and dodecanoic acid, and their branched fatty acids, such as 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; Can be When the number of carbon atoms is less than 6, an unpleasant odor becomes strong, and when the number is more than 12, foaming becomes large, which is not preferable. If the amount is less than 0.1% by weight, it will be difficult to maintain a stable liquid state. If the amount is more than 20% by weight, the degreasing power will decrease, the amount of residue will increase when water rinsing is not required, painting, etc. Is unfavorably affected.
[0012]
Examples of the dicarboxylic acid having 6 to 18 carbon atoms include adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,9-nonamethylenedicarboxylic acid, 1,10-decamethylenedicarboxylic acid, and 1,11-undecamethylenedicarboxylic acid. 1,12-dodecamethylenedicarboxylic acid, 1,13-tridecamethylenedicarboxylic acid, 1,14-tetradecamethylenedicarboxylic acid, 1,15-pentadecamethylenedicarboxylic acid, and 1,16-hexadecamethylenedicarboxylic acid No. If the number of carbon atoms is less than 6, the rust-proofing property against iron becomes inferior. If the number is more than 18, the residue when used without water rinsing tends to be in a solid state, which is not preferable. If the amount is less than 0.1% by weight, the rust-preventing property is deteriorated. If the amount is more than 20% by weight, the amount of the residue is increased when water rinsing is unnecessary and the solidification is not preferable.
[0013]
Water is used as a solvent for making a detergent active ingredient such as morpholine, polyoxyethylene polyoxypropylene block polymer, fatty acid, dicarboxylic acid and the like into a uniform liquid product. The amount is determined such that the total amount of water and the amounts of the above-mentioned cleaning agent active ingredients and known additives and the like become 100% by weight.
The pH of the cleaning agent is adjusted to 7 to 9.5, preferably 7 to 9, more preferably 7 to 8.5. If it is lower than 7, the stability to iron will be inferior, and if it is higher than 9.5, the stability to aluminum will be inferior, and the irritation to the skin will be too strong.
When the cleaning agent of the present invention is used in an actual cleaning step, it is further diluted with water. The concentration of the detergent active ingredient at that time is usually 0.005 to 5% by weight. The concentration of the detergent active ingredient is appropriately adjusted depending on conditions such as a cleaning method, a cleaned article, a stain, and a post-process.
[0014]
In the present invention, other surfactants, known additives, for example, chelating agents such as gluconate, ethylenediaminetetraacetate, nitrilotriacetate, benzotriazole, amines, corrosion inhibitors such as nitrite, Antifoaming agents such as fatty oil and silicone oil, ethylene glycol monoalkyl ether, ethylene glycol monophenyl ether, diethylene glycol monoalkyl ether, diethylene glycol monophenyl ether, triethylene glycol monoalkyl ether, triethylene glycol monophenyl ether, propylene glycol mono Alkyl ether, propylene glycol monophenyl ether, dipropylene glycol monoalkyl ether, dipropylene glycol monophenyl ether, tripropylene glycol Monoalkyl ether, tripropylene glycol monophenyl ether, etc., wherein the alkyl group is a linear, branched, or cyclic glycol ether having 1 to 8 carbon atoms, methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, It is also possible to appropriately mix and use alcohols such as t-butanol, n-amyl alcohol, isoamyl alcohol, s-amyl alcohol, t-amyl alcohol and benzyl alcohol, and solvents such as pyrrolidone and N-methylpyrrolidone.
[0015]
【Example】
Hereinafter, the present invention will be described with reference to examples.
(Examples 1 to 5 and Comparative Examples 1 to 3 )
The cleaning agents shown in Table 1 were blended, and the following tests were performed. Table 2 shows the results.
(1) Degreasing test A 30-mesh stainless steel mesh (60 × 30 mm) was impregnated with the following metal working oil and heated at 100 ° C. for 30 minutes. This was washed with a 3% by weight aqueous solution of the detergent shown in Table 1, dried without rinsing with water, and the degreasing rate was calculated from the amount of oil adhering before and after washing by the following equation 1, and 1,1,1-trichloroethane was obtained. Comparative evaluation with degreasing by
Metal working oil used for the test: Unicut GH35 (trade name, manufactured by Nippon Oil Co., Ltd.)
[0016]
(2) Stability test The detergents shown in Table 1 were kept at 30 ° C. and 50 ° C., and observations were made for the separation and precipitation of the active ingredients of the detergent.
(3) Evaporation residue test 0.3 μl of a 3% by weight aqueous solution of the detergent shown in Table 1 was dropped on a hole slide glass, dried at 120 ° C. for 30 minutes, and the properties of the residue were evaluated.
(4) Coating adhesion test The aluminum plate was washed with a 3% by weight aqueous solution of the cleaning agent in Table 1, dried without rinsing with water, and then coated with lacquer. The adhesion of the coating film was determined by a cross cut test of JIS K5400 (100 squares of 1 mm square).
(5) Rust prevention test Iron (SC46) was immersed in a 3% by weight aqueous solution of the cleaning agent in Table 1 and kept at 50 ° C for 4 hours, and then the presence or absence of rust generation was determined.
[0017]
(Equation 1)

[0018]
[Table 1]

[0019]
[Table 2]

[0020]
【The invention's effect】
The present invention is a stable liquid excellent cleaning agent which has a degreasing power comparable to that of a chlorine-based solvent and can be used without the need for water rinsing.

Claims (1)

At least (1) morpholine 0.1 to 20% by weight
(2) Polyoxyethylene polyoxypropylene block polymer 0.1 to 10% by weight
(3) aliphatic acid having 6 to 12 carbon atoms 0.1 to 20% by weight
(4) 0.1 to 20% by weight of dicarboxylic acid having 6 to 18 carbon atoms
(5) A cleaning agent comprising water and having a pH of 7 to 9.5.