JPH0881698A - Detergent composition - Google Patents

Abstract

(57) [Summary] [Purpose] Overcoming the disadvantages of conventional halogen-based detergents and alkyl lactate-based alternative detergents, it has low toxicity, high safety, and excellent environmental protection. An object of the present invention is to provide a detergent composition having excellent operability and excellent solubility and releasability of substances and the like. [Constitution] α-alkoxyisobutyric acid alkyl ester,
A detergent composition comprising at least one oxyisobutyric acid ester selected from β-alkoxyisobutyric acid alkyl ester and α-hydroxyisobutyric acid alkyl ester and an aliphatic hydrocarbon as active ingredients.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition, and more particularly to degreasing cleaning of metal, resin, glass, ceramics, precision equipment, electrical parts, electronic parts, optical parts, etc., resist ink, offset. Ink, gravure ink, silk screen ink, flexo ink,
The present invention relates to a cleaning composition suitable for peeling off and cleaning various ink films such as oil-based markers, cleaning and removing stains and adhered liquid crystals of liquid crystal cells. The cleaning composition of the present invention can be used in various fields such as machine industry, plastics industry, printing industry, coating industry and electronic industry.

[0002]

2. Description of the Related Art In the industries involving processing of metal parts such as machine industry, precision machine industry, automobile industry, electronics industry, electric industry, plastic processing industry, optical industry, plastic parts and glass parts such as lenses, In order to perform the work smoothly and efficiently in the manufacturing process or to improve the processing accuracy, various oils and fats such as cutting oil, processing oil, press oil, rust preventive oil, lubricating oil, grease or pitch are used. It is used appropriately in the process.

Usually, when the surface of glass such as metal, plastic or lens is plated, vapor-deposited, painted or coated, or before being shipped as a product, oils and fats used in the previous process and adhering to the surface It is necessary to wash away dirt and stains to get a clean surface. However, the properties of oils and fats differ greatly depending on the type of application, for example,
Solubility in solvents varies greatly depending on the composition of components, viscosity, additives, etc.Therefore, a detergent with a strong dissolving power is required to have a detergency that can be applied to any oil or fat. It

In the fields of various printing, electronic circuit board manufacturing, instrument board manufacturing, and the like, various inks have been developed and used in order to improve weather resistance, workability, or accuracy. Ink has a detergency that can be applied to any ink because its solubility in solvent is very different depending on its type, for example, the type of base polymer or the type of curing mechanism such as UV curing, heat curing or evaporation curing. Therefore, a cleaning agent having a strong dissolving power is required.

Conventionally, as these detergents, methylchloroform (1,1,1-trichloroethane), trichloroethylene or freon 113, which has a high dissolving power, is used.
Those containing halogenated hydrocarbons such as (1,1,2-trichloro-1,2,2-trifluoroethane) as a main agent have been widely used. In particular, CFC 113 has been widely used because it is nonflammable, has low toxicity, is excellent in stability, and has a property of selectively dissolving various stains without invading metals, plastics, elastomers and the like. However, freon 113 and methylchloroform destroy the ozone layer in the stratosphere and eventually cause the development of skin cancer, so that their use is being rapidly restricted. Moreover, the use of trichlorethylene is suspected to be carcinogenic, and its use is being restricted from the viewpoint of safety.

Therefore, an alternative CFC-based cleaning agent having a cleaning property that can replace CFC 113 and the like, and having no fear of ozone layer depletion is being actively developed. For example, 1,2
-Containing difluoroethane as a main component (JP-A-1-1
No. 32694), 1,1-dichloro-2,2,2-
Many alternative CFCs have been proposed, such as a mixture of trifluoroethane and dimethoxymethane (JP-A-2-178396) and one containing hexafluorobenzene as a main component (JP-A-3-167298). But,
These cleaning agents do not reach the level of CFC 113 in terms of performance, and in the future, these halogen-based solvents are in the direction of usage restrictions due to environmental and safety issues, so they are far from an essential solution. .

On the other hand, as a cleaning agent for degreasing, which is highly safe for the human body and does not cause environmental damage, a cleaning agent containing a nonionic surfactant and an alkyl lactate as main components (Japanese Patent Laid-Open No. 4-6).
No. 8088), those containing a nonionic surfactant and an adipic acid ester as main components (JP-A-4-59985), those containing a nonionic surfactant and a polyalkylene glycol dialkyl ether as main components (JP-A No. 4-59985). −
No. 59984), those containing a nonionic surfactant and N-methylpyrrolidone as main components (JP-A-4-680).
94), those containing nonionic surfactants and glycerine acetates as main components (JP-A-4-68092), those containing alcohols and fatty acid esters as main components (JP-A-4-68090). There is a suggestion such as.
Alkyl lactate, N-methylpyrrolidone and the like are highly safe solvents with low toxicity and no environmental damage or accumulation. However, as is clear from the above patent comparative examples, the solvent alone can be used for fats and oils. It is still unsatisfactory as a degreasing detergent because of its insufficient dissolving power and the necessity of using a cleaning aid such as a surfactant in combination.

Further, as an ink cleaning agent which is highly safe to the human body and which does not cause environmental damage, a cleaning agent containing an alkyl lactate ester as a main component has been proposed (JP-A-3-4117).
No. 0). Alkyl lactate is a highly safe solvent with low toxicity and no environmental damage or environmental accumulation, but its solubility in polymer inks is insufficient, and it is still satisfactory as an ink cleaner. is not.

[0009]

As described above, in the technical field of the present invention, a non-halogen solvent is used as a main component, and there is no toxicity or safety problem to the human body, and the emission of environmentally destructive substances into the air and water systems. It has become an important issue to develop a detergent that does not accumulate in the environment, has no accumulation in the environment, and has a high dissolving power for various oils and fats and various printing inks.

The present invention overcomes the drawbacks of the conventional halogen-based detergents and alkyl lactate-based alternative detergents as described above, is composed of a solvent system of low toxicity and is safe, and is used for various oils and fats and various inks. It has been made for the purpose of providing a detergent composition which has a high cleaning ability for, etc., does not generate environmentally destructive substances, has no unpleasant odor, has a relatively high boiling point, is safe, and has good operability. .

[0011]

As a result of intensive studies to develop a detergent composition having the above-mentioned preferable properties, the present inventors have found that α-alkoxyisobutyric acid alkyl ester and β-alkoxyisobutyric acid alkyl ester. The present inventors have found that esters and mixtures of branched oxyisobutyric acid esters such as α-hydroxyisobutyric acid alkyl esters and aliphatic hydrocarbons have remarkably good cleaning performance and meet the purpose, and arrived at the present invention.

That is, the present invention provides the following general formula [1]:
Α-alkoxyisobutyric acid alkyl ester represented by

Embedded image

Embedded image β-alkoxyisobutyric acid alkyl ester represented by the following general formula [2] And an alkyl ester of α-hydroxyisobutyric acid represented by the following general formula [3]

[Chemical 3] (However, in the above formulas, R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms.) At least one oxyisobutyric acid ester and an aliphatic hydrocarbon are contained as active ingredients. Cleaning composition.

Hereinafter, the present invention will be described in detail. It is important that the detergent composition of the present invention contains oxyisobutyric acid esters and aliphatic hydrocarbons. As the oxyisobutyric acid ester, α-alkoxyisobutyric acid alkyl esters such as methyl α-methoxyisobutyrate, ethyl α-methoxyisobutyrate, methyl α-ethoxyisobutyrate, ethyl α-ethoxyisobutyrate (corresponding to general formula [1]); β -Β-alkoxyisobutyric acid alkyl esters such as methyl methoxyisobutyrate, ethyl β-methoxyisobutyrate, methyl β-ethoxyisobutyrate and ethyl β-ethoxyisobutyrate (corresponding to general formula [2]); and α-hydroxyisobutyrate, α-Hydroxyisobutyric acid alkyl esters such as ethyl α-hydroxyisobutyrate (corresponding to the general formula [3]) can be mentioned, and in particular, methyl α-methoxyisobutyrate, methyl β-methoxyisobutyrate, methyl β-ethoxyisobutyrate, or α -Methyl hydroxyisobutyrate was found to have And is preferable in terms of volatility.

These α-alkoxyisobutyric acid alkyl esters (corresponding to general formula [1]), β-alkoxyisobutyric acid alkyl esters (corresponding to general formula [2]) and α
-Hydroxyisobutyric acid alkyl ester (general formula [3]
May be used alone or in combination of two or more.

The aliphatic hydrocarbons used in the present invention include pentane, hexane, heptane, octane, nonane, decane, which have a boiling point in the range of 30 ° C to 300 ° C.
Linear paraffins such as dodecane; 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, isoparaffins such as 2-methylhexane and isooctane, 2-pentene, 1-hexene, 1-heptene, Olefins such as 1-octene, 1-nonene and 1-decene; and naphthenes such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, P-menthane, bicyclohexyl, cyclohexene, α-pinene, dipentene and decalin. Can be mentioned. These aliphatic hydrocarbons can be used in combination of two or more kinds. Further, a petroleum fraction such as petroleum ether, petroleum benzine, petroleum naphtha, ligroin, industrial gasoline, and kerosene, petroleum fraction such as isoparaffin or naphthene, or synthetic hydrocarbon fraction may be used as a mixture.

The proportion of oxyisobutyric acid esters and aliphatic hydrocarbons used in the present invention is 5:95 to 9 by weight.
5: 5, preferably 10:90 to 90:10.

The α-alkoxyisobutyric acid alkyl ester, β-alkoxyisobutyric acid alkyl ester and α-hydroxyisobutyric acid alkyl ester used in the present invention are alcohols, esters, ketones, amides, other general organic solvents such as aromatics. They are well compatible with each other, and not only ordinary organic compounds but also natural resins such as cellulosic resins, epoxy resins, acrylic resins, vinyl resins, alkyd resins,
It has excellent solubility in a wide range of high molecular compounds such as synthetic resins such as polyester resins and novolac resins. Therefore, the detergent composition of the present invention may be used as it is, but it also exhibits excellent performance as a mixture in which other general organic solvents are used in combination, and oxyisobutyric acid ester, an aliphatic hydrocarbon, and an organic solvent. It can also be used as a detergent mixture containing.

The general solvent used in combination is not particularly limited and can be widely used in alcohols, ethers, esters, ketones, amides, aromatic hydrocarbons and the like, but preferred examples are: Isopropanol, butanol, methylisobutylcarbinol, propylene glycol, heptanol, octanol, nonanol, 3-methylbutanol, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 3, 5, 5
-Trimethyl-1-hexanol, 2-ethyl-1-hexanol, cyclohexanol, benzyl alcohol, methyl isobutyl ketone, cyclohexanone, isophorone, acetophenone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, methyl acetate, ethyl acetate, butyl acetate , Amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate,
Examples include methyl β-methoxypropionate, ethyl 3-ethylpropionate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, dibenzyl ether, tetrahydrofuran, dioxane, dioxolane, propylene glycol monomethyl ether acetate, toluene, xylene and tetralin. . These organic solvents can be used in combination of two or more kinds. The use amount of these organic solvents is 70% by weight or less, preferably 50% by weight or less of the detergent composition.

In order to improve the detergency, a surfactant such as a nonionic surfactant, an anionic surfactant or a cationic surfactant, and an acidic compound or a basic compound may be used in combination. You can also

The preferred contents of the α-alkoxyisobutyric acid alkyl ester, the β-alkoxyisobutyric acid alkyl ester, and the α-hydroxyisobutyric acid alkyl ester in the detergent composition of the present invention vary depending on the use and formulation thereof. Usually, it is preferably at least 5% by weight, particularly preferably 10% by weight or more.

[0021]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Examples 1 to 15 Commercially available inks A to D shown below were uniformly applied to an aluminum plate (50 × 20 × 2 mm) whose surface was polished by a bar coder and used as a test piece. A: Instrument plate character ink (green, cellulose resin type) B: Solder resist ink (green, thermosetting type) C: Marking ink (white, UV curing type) D: Screen printing ink (white, salt-based acrylic) One hour after the ink was applied, the test piece was placed in a cleaning bottle containing an ink cleaning composition of the present invention, shaken at room temperature for 30 seconds, dried, and then the residual adhesion amount was measured and evaluated. . The residual adhesion amount was measured visually and with a metallurgical microscope. ◯: No residual deposits visually or by a metallurgical microscope. Δ: No residual deposits visually, but with a metallurgical microscope. X: Remaining deposits are visually observed. The results are shown in Tables 1 and 2.

[0023]

[Table 1]

[0024]

[Table 2]

Comparative Examples 1 to 4 Examples 1 to 1 except that an ink cleaning agent having a conventional composition was used.
An evaluation test was conducted in the same manner as in 5. The results are shown in Table 3.

[0026]

[Table 3]

Examples 16 to 28 Stainless steel plates (50 × 20 × 2 mm) whose surfaces were polished were uniformly coated with commercially available fats and oils A to C shown below and used as test pieces. A: Cutting oil (made by Idemitsu Kosan, Daphne Marg Plus L
A15) B: Press oil (manufactured by Nippon Oil Co., Unipres DP12
0) C: Grease (Showa Shell Sekiyu Co., Ltd., Albania Grease 1) One hour after the application of the oil and fat, the test piece was put into a cleaning bottle containing a degreasing cleaning agent having the composition of the present invention, and 40
After shaking at 5 ° C for 5 minutes and drying with hot air, the residual adhesion amount was measured and evaluated. The residual adhesion amount was measured visually and with a metallurgical microscope. ◯: No residual deposits visually or by a metallurgical microscope. Δ: No residual deposits visually, but with a metallurgical microscope. X: Remaining deposits are visually observed. The results are shown in Tables 4 and 5.

[0028]

[Table 4]

[0029]

[Table 5]

Comparative Examples 5 to 8 Table 6 shows the results of an evaluation test carried out in the same manner as in Examples except that the conventional degreasing detergent was used.

[0031]

[Table 6]

[0032]

The cleaning composition of the present invention is extremely excellent in cleanability and peelability, has no problems in environmental protection, and has high safety. Further, the present invention has the following advantages. (1) It has extremely high solubility in various oils and fats and inks. (2) The solubility of natural and synthetic polymers is extremely high, and the exfoliation and removability of oils, greases, and inks are excellent. (3) It can be freely mixed with many organic solvents and mixed for use. (4) It is water-soluble and can be used in an aqueous system. (5) It is biodegradable and does not accumulate in nature. (6) Low toxicity and high safety. (7) The boiling point and the flash point are relatively high, and the operability and safety are significantly improved. (8) Does not attack the base material.

Claims (4)

[Claims] 1. An α-alkoxyisobutyric acid alkyl ester represented by the following general formula [1]: Embedded image β-alkoxyisobutyric acid alkyl ester represented by the following general formula [2] And an α-hydroxyisobutyric acid alkyl ester represented by the following general formula [3]: (However, in the above formulas, R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms.) At least one oxyisobutyric acid ester and an aliphatic hydrocarbon are contained as active ingredients. A cleaning composition. 2. An oxyisobutyric acid ester is methyl α-methoxyisobutyrate, ethyl α-methoxyisobutyrate or α-methoxyisobutyrate.
Methyl ethoxyisobutyrate, ethyl α-ethoxyisobutyrate, methyl β-methoxyisobutyrate, ethyl β-methoxyisobutyrate, methyl β-ethoxyisobutyrate, ethyl β-ethoxyisobutyrate, methyl α-hydroxyisobutyrate, or ethyl α-hydroxyisobutyrate. The cleaning composition according to claim 1. 3. The aliphatic hydrocarbons have a boiling point of 30.degree.
The cleaning composition according to claim 1 or 2, which is at least one selected from the group consisting of linear paraffin, isoparaffin, olefin and naphthene in the range of 00 ° C. 4. The at least one oxyisobutyric acid ester and the aliphatic hydrocarbons, in addition to isopropanol, butanol, methylisobutylcarbinol, propylene glycol, heptanol, octanol, nonanol, 3-methylbutanol, 3-methoxybutanol,
3-methyl-3-methoxybutanol, 3,5,5-trimethyl-1-hexanol, 2-ethyl-1-hexanol, cyclohexanol, benzyl alcohol, methyl isobutyl ketone, cyclohexanone, isophorone, acetophenone, N-methylpyrrolidone, Dimethylformamide, dimethylacetamide, methyl acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate,
3-methyl-3-methoxybutyl acetate, methyl β-methoxypropionate, ethyl 3-ethylpropionate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, dibenzyl ether,
The cleaning composition according to claim 1, 2 or 3, further comprising at least one compound selected from the group consisting of tetrahydrofuran, dioxane, dioxolane, propylene glycol monomethyl ether acetate, toluene, xylene and tetralin.