JP2951216B2 - 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 a cleaning composition, and more particularly to degreasing cleaning of metals, resins, glass, ceramics, precision instruments, electric parts, electronic parts, optical parts, etc., resist ink, offset. Ink, gravure ink, silk screen ink, flexo ink,
The present invention relates to a detergent composition suitable for peeling and washing various ink films such as oily markers and the like, and washing and removing dirt and adhered liquid crystal of liquid crystal cells. The cleaning composition of the present invention can be used in various fields such as a machine industry, a plastic industry, a printing industry, a paint industry, and an electronics industry.

[0002]

2. Description of the Related Art In the industries that involve the processing of glass parts such as metal parts, plastic parts, and lenses, such as the machine industry, precision machine industry, automobile industry, electronic industry, electric industry, plastic processing industry, and optical industry, Various oils and fats such as cutting oil, processing oil, press oil, rust-preventive oil, lubricating oil, grease, pitch, etc. are used for smooth and efficient work in the manufacturing process or for improving the processing accuracy. It is appropriately used in the process.

[0003] Generally, when plating, vapor deposition, painting or coating on the surface of glass such as metal, plastic or lens, or before shipping as a product, oils and fats used in previous processes and adhering to the surface It is necessary to wash and remove dirt and dirt to obtain a clean surface. However, the properties of fats and oils vary greatly depending on the type and use, for example,
Solubility in solvents is very different due to differences in the composition, viscosity, additives, etc. of the components, so a detergent with strong dissolving power is required to have a detergency that can be applied to any fats and oils. You.

[0004] In the fields of various printing, electronic circuit board production, instrument panel production, and the like, various inks have been developed and used to improve weather resistance, workability, and accuracy. Since inks have very different solubility in solvents depending on their type, for example, type of base polymer or type of curing mechanism such as ultraviolet curing, thermal curing or evaporative curing, they have a detergency that can be applied to any ink. For this purpose, a cleaning agent having a strong dissolving power is required.

Conventionally, these detergents include methyl chloroform (1,1,1-trichloroethane), trichloroethylene or chlorofluorocarbon 113, which have a large dissolving power.
Those based on halogenated hydrocarbons such as (1,1,2-trichloro-1,2,2-trifluoroethane) have been widely used. In particular, CFC 113 has been widely used because it is nonflammable, has low toxicity, has excellent stability, and does not attack metals, plastics, elastomers and the like and selectively dissolves various kinds of stains. However, their use is rapidly being restricted because CFCs 113 and methylchloroform destroy the stratospheric ozone layer and eventually cause skin cancer. In addition, use of trichlorethylene is also being restricted from the viewpoint of safety, for example, due to suspected carcinogenicity.

[0006] For this reason, development of an alternative fluorocarbon-based cleaning agent having a detergency that can substitute for fluorocarbon 113 or the like and having no fear of destruction of the ozone layer is being actively conducted. For example, 1, 2,
Those containing difluoroethane as a main component (Japanese Unexamined Patent Publication (Kokai) No. 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 a mixture containing hexafluorobenzene as a main component (JP-A-3-167298). But,
The performance of these cleaning agents does not reach that of CFC 113, and the use of these halogen-based solvents in the future is being restricted in view of environmental and safety issues, so that they are far from an essential solution. .

On the other hand, as a degreasing detergent which is highly safe to the human body and has no environmental destruction, a detergent 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 ester as main components (Japanese Patent Application Laid-Open No. 4-59985), those containing a nonionic surfactant and a polyalkylene glycol dialkyl ether as main components (Japanese Patent Application Laid-Open No. −
No. 59,984), those containing a nonionic surfactant and N-methylpyrrolidone as main components (JP-A-4-680).
No. 94), those containing a nonionic surfactant and glycerin acetate as main components (JP-A-4-68092) and those containing alcohol and fatty acid ester as main components (JP-A-4-68090). There are proposals such as.
Alkyl lactate, N-methylpyrrolidone, etc. have low toxicity and are very safe solvents without environmental destruction or environmental accumulation. However, as is clear from the above-mentioned patent comparative examples, the solvent alone is not suitable for oils and fats. It has not been satisfactory as a cleaning agent for degreasing, because its dissolving power is insufficient and it is essential to use a cleaning aid such as a surfactant in combination.

[0008] Further, there has been proposed an ink detergent containing alkyl lactate as a main component as a highly safe to the human body and without environmental destruction (Japanese Patent Laid-Open No. 3-4117).
No. 0). Alkyl lactate is a very safe solvent with low toxicity and no environmental destruction or environmental accumulation.However, it has insufficient dissolving power for polymer inks and is still satisfactory as an ink cleaner. is not.

[0009]

As described above, in the technical field of the art, non-halogen solvents are the main components, and there are no problems in toxicity and safety to the human body, and emission of environmental destructive substances to the air and water systems. The development of a cleaning agent which has no dissolution, does not accumulate in the environment, and has a high dissolving power in various oils and fats, various printing inks and the like has become an important issue.

The present invention overcomes the drawbacks of the conventional halogen-based detergents and alkyl lactate-based alternative detergents as described above, and comprises a low-toxicity and safe solvent system, various oils and fats, and various inks. The purpose of the present invention is to provide a cleaning composition having a high cleaning ability, no generation of environmentally destructive substances, no unpleasant odor, a relatively high boiling point, and good operability. .

[0011]

The present inventors have conducted intensive studies to develop a detergent composition having the above-mentioned preferable properties, and as a result, have found that alkyl α-alkoxyisobutyrate and alkyl β-alkoxyisobutyrate have been obtained. Esters, mixtures of oxyacid esters such as alkyl esters of α-hydroxyisobutyric acid and alkyl esters of β-alkoxypropionic acid and aromatic oxygenates have remarkably good cleaning performance and are found to be suitable for that purpose, The present invention has been reached.

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

Embedded image Β-alkoxyisobutyric acid alkyl ester represented by the following general formula [2]

Embedded image Α-hydroxyisobutyric acid alkyl ester represented by the following general formula [3]

Embedded image And a β-alkoxypropionic acid alkyl ester represented by the following general formula [4]:

Embedded image R ¹ OCH ₂ CH ₂ CO ₂ R ² Formula (4) (wherein R ¹ and R ² each represent an alkyl group having 1 to 4 carbon atoms). A cleaning composition comprising at least one oxyacid ester and an aromatic oxygen-containing compound as active ingredients.

Hereinafter, the present invention will be described in detail. It is important that the cleaning composition of the present invention contains oxyacid esters and aromatic oxygen-containing compounds. Examples of the oxyisobutyrate include alkyl α-alkoxyisobutyrate (equivalent to general formula [1]) such as methyl α-methoxyisobutyrate, ethyl α-methoxyisobutyrate, methyl α-ethoxyisobutyrate, and ethyl α-ethoxyisobutyrate; β Alkyl esters of β-alkoxyisobutyrate such as methyl-methoxyisobutyrate, ethyl β-methoxyisobutyrate, methyl β-ethoxyisobutyrate, ethyl β-ethoxyisobutyrate (corresponding to the general formula [2]); methyl α-hydroxyisobutyrate, α Α-hydroxyisobutyric acid alkyl esters such as ethyl-hydroxyisobutyrate (corresponding to the general formula [3]); and β-alkoxypropionic acid alkyl esters such as methyl β-methoxypropionate and ethyl β-ethoxypropionate ( (Equivalent to general formula [4]). -Methyl methoxyisobutyrate,
Methyl β-methoxyisobutyrate, methyl β-ethoxyisobutyrate, methyl α-hydroxyisobutyrate or methyl β-methoxypropionate are preferred from the viewpoints of dissolving power stripping ability and volatility.

These alkyl esters of α-alkoxyisobutyric acid (corresponding to the general formula [1]) and alkyl esters of β-alkoxyisobutyric acid (corresponding to the general formula [2]) α-hydroxyisobutyric acid alkyl esters (of the general formula [3] ] And alkyl esters of β-alkoxypropionic acids (corresponding to general formula [4]) may be used alone or
Also, two or more kinds may be used in combination.

The aromatic oxygen-containing compounds used in the present invention are selected from aromatic ketones, aromatic ethers and aromatic esters. Specifically, acetophenone, propiophenone, benzophenone, diphenyl ether,
Dibenzyl ether, benzyl methyl ether, benzyl ethyl ether, anisole, phenetole, butyl phenyl ether, methoxytoluene, benzyl acetate,
Benzyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, isoamyl benzoate, benzyl benzoate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, methyl cinnamate, ethyl cinnamate, etc. Is mentioned. These aromatic oxygen-containing compounds may be used alone or in combination of two or more.

The ratio of the oxyacid ester to the aromatic oxygen-containing compound used in the present invention is from 5:95 to 9 by weight.
5: 5, preferably from 10:90 to 90:10.

The alkyl α-alkoxyisobutyrate, alkyl β-alkoxyisobutyrate, alkyl α-hydroxyisobutyrate and alkyl β-alkoxypropionate used in the present invention are:
Alcohols, esters, ketones, amides, aromatics and other common organic solvents are well compatible, and, in addition to ordinary organic compounds, natural resins such as cellulose resins and epoxy resins, acrylic resins, vinyl resins, alkyd resins, It has extremely good solubility even in a wide range of polymer compounds such as polyester resins and synthetic resins such as novolak resins. For this reason, the cleaning 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 oxyisobutyrate, an aliphatic hydrocarbon, an organic solvent and Can also be used as a detergent mixture.

The general solvent to be used in combination is not particularly limited, and can be widely used such as alcohols, ethers, esters, ketones, amides, and aromatic hydrocarbons. Isopropanol, butanol, methyl isobutylcarbinol, 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, 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, 2-ethylhexyl acetate, cyclohexyl acetate, tetrahydrofuran, dioxane, dioxolan, propylene glycol monomethyl ether acetate , Toluene, xylene and tetralin. These organic solvents can be used in combination of two or more kinds. The amount of these organic solvents used is 80% by weight of the detergent composition.
Or less, preferably 70% by weight or less.

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

The preferred content of the alkyl α-alkoxyisobutyrate, the alkyl β-alkoxyisobutyrate, the alkyl α-hydroxyisobutyrate and the alkyl β-alkoxypropionate in the detergent composition of the present invention depends on the use thereof. Usually, it is preferably at least 5% by weight or more, particularly preferably at least 10% by weight, although it depends on the composition and the like.

[0021]

EXAMPLES Hereinafter, the present invention will be specifically described 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 of the following A to D were uniformly coated on a surface-polished aluminum plate (50 × 20 × 2 mm) with a bar coder and used as test pieces. A: Ink for instrument panel text (green, cellulose resin type) B: Solder resist ink (green, thermosetting type) C: Marking ink (white, ultraviolet curable type) D: Screen printing ink (white, polyvinyl chloride acrylic type) One hour after the application of the ink, the test piece was put into a washing bottle containing the ink detergent of the present invention, shaken at room temperature for 30 seconds, dried, and the remaining adhesion amount was measured and evaluated. . In addition, the measurement of the residual adhesion amount was determined visually and with a metallographic microscope. : No residual matter was observed visually and with a metallographic microscope. Δ: No residual deposit visually, but with a metallographic microscope. ×: Residual deposits were 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 were repeated except that a conventional ink cleaning agent was used.
An evaluation test was performed in the same manner as in Example 5. Table 3 shows the results.

[0026]

[Table 3]

Examples 16 to 28 Commercially available fats and oils of the following A to C were uniformly applied to a stainless plate (50 × 20 × 2 mm) whose surface was polished, and used as a test piece. A: Cutting oil (made by Idemitsu Kosan, Daphne Marg Plus L
A15) B: Press oil (Nippon Oil, Unipres DP12)
0) C: Grease (Showa Shell Sekiyu Kabushiki Kaisha, Albania Grease 1) One hour after applying the fat, a test piece was put into a cleaning bottle containing a degreasing detergent of the present invention,
After shaking at 5 ° C. for 5 minutes, the resultant was dried with hot air, and the amount of remaining adhesion was measured and evaluated. In addition, the measurement of the residual adhesion amount was determined visually and with a metallographic microscope. : No residual matter was observed visually and with a metallographic microscope. Δ: No residual deposit visually, but with a metallographic microscope. ×: Residual deposits were 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 conducted in the same manner as in the Examples except that the conventional degreasing detergent was used.

[0031]

[Table 6]

[0032]

The cleaning composition of the present invention is extremely excellent in detergency and releasability, has no environmental problems, and has high safety. Further, the present invention has the following advantages. (1) Very high solubility in various fats and oils and inks. (2) The solubility of natural and synthetic polymers is extremely high, and the oils, greases, and inks are excellent in removal and removal properties. (3) It can be freely mixed with many organic solvents and used in a mixed manner. (4) It is water-soluble and can be used in aqueous systems. (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 substrate.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-B Hei 3-22619 (JP, B2) “Chemical Industry Daily”, June 24, 1994, Edition B (58) Fields surveyed (Int. Cl. ⁶ , DB name) C11D 7/26 C11D 7/50 C11D 3/20 C11D 3/43-3/44 CA (STN) WPI / L (QUESTEL)

Claims (4)

(57) [Claims] 1. An α-alkoxyisobutyric acid alkyl ester represented by the following general formula [1]: OR 1 | (CH 3) 2 CCO 2 R 2 formula [1] The following general formula [2] Β-alkoxyisobutyric acid alkyl ester represented by the following formula: CH3 | R1 OCH2 CHCO2 R2 Formula [2] α-hydroxyisobutyric acid alkyl ester represented by the following general formula [3]: OH | (CH 3) 2 CCO 2 R 2 ----- β-alkoxypropionic acid alkyl ester represented by the formula [3] and the following general formula [4]: R 1 OCH 2 CH 2 CO 2 R 2- --- Formula [4] (wherein, R1 and R2 in the above formulas each have 1 to 4 carbon atoms)
Represents an alkyl group. ) At least one oxyacid ester selected from aromatic ketones, aromatic ethers and
At least one selected from the group consisting of
Degreasing, ink cleaning and detergent compositions for cleaning liquid crystal cell, characterized in that it comprises species of aromatic oxygen-containing compounds as an active ingredient. 2. The method according to claim 1, wherein the oxyacid ester is methyl α-methoxyisobutyrate, ethyl α-methoxyisobutyrate, methyl α-ethoxyisobutyrate, ethyl α-ethoxyisobutyrate, β-
With methyl methoxyisobutyrate, ethyl β-methoxyisobutyrate, methyl β-ethoxyisobutyrate, ethyl β-ethoxyisobutyrate, methyl α-hydroxyisobutyrate, ethyl α-hydroxyisobutyrate, methyl β-methoxypropionate or ethyl β-ethoxypropionate. Certain claim 1
The cleaning composition according to the above. 3. The aromatic oxygen-containing compounds are acetophenone, propiophenone, benzophenone, diphenyl ether, dibenzyl ether, benzyl methyl ether, benzyl ethyl ether, anisole, phenetole, butyl phenyl ether, methoxytoluene, benzyl acetate, and propion. Consists of benzyl acrylate, methyl benzoate, ethyl benzoate, propyl benzoate, isoamyl benzoate, benzyl benzoate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, methyl cinnamate and ethyl cinnamate 3. The cleaning composition according to claim 1, which is at least one member selected from the group. 4. The method according to claim 1, wherein the at least one oxyacid ester and the aromatic oxygenates include 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, 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, 2-ethylhexyl acetate,
4. The cleaning composition according to claim 1, further comprising at least one compound selected from the group consisting of cyclohexyl acetate, tetrahydrofuran, dioxane, dioxolan, propylene glycol monomethyl ether acetate, toluene, xylene and tetralin.