JPH09291300A - Detergent composition and cleaning - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent composition useful for removing stain of various articles, capable of maintaining excellent cleaning and drying properties, low cost, safety to human body and environmental preservation for a long period of time, free from deterioration by heat, comprising a specific hydrocarbon and a specific amount of an alkylmonophenol. SOLUTION: This detergent comprises (A) a 5-15C hydrocarbon [e.g. a isoparaffin containing a group of the formula (R1 , R2 and R3 are each an alkyl) (preferably a 8-12C isoparaffine having distillation properties of 95% distillation temperature within 5 deg.C from an initial boiling point and 99% distillation temperature within 10 deg.C from the initial boiling point), a naphthene, an alkylbenzene or their mixture and (B) 0.001-1wt.% of an alkylmonophenol (e.g. 2,6-di-t-butyl-p- cresol or 2,4,6-tri-t-butylphenol).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition for removing dirt components from an article and a cleaning method using the same, and more particularly to a detergent composition which is not deteriorated by heat and the cleaning composition. The cleaning method that was used.

[0002]

2. Description of the Related Art Conventionally, mechanical parts have been cleaned of their contaminants by dipping with a chlorine-based solvent such as 1,1,1-trichloroethane, trichloroethylene, or ethylene chloride, ultrasonic vibration, or rotating barrel. . On the other hand, for electric and electronic parts and optical characteristics, a stain component is mainly removed by using a chlorine-based solvent such as 1,1-trichloroethane or Freon 113 or a Freon-based solvent.

However, in recent years, these detergents have been replaced from the viewpoint of the global environment or safety. As this alternative detergent, for example, an aqueous detergent comprising a surfactant and a builder, amines such as glycol ethers and N-methylpyrrolidone, or detergents containing terpenes such as limonene as a main component are proposed. ing. Further, a cleaning agent containing a hydrocarbon as a main component is widely used from the viewpoints of global environment, human safety cost, and detergency. Further, various cleaning methods have been proposed which solve the drawbacks of the detergent containing hydrocarbon as a main component, that is, the high flammability and the poor dryness.

For example, Japanese Unexamined Patent Publication (Kokai) No. 5-43893 proposes a cleaning composition for precision parts comprising a hydrocarbon fraction whose boiling point range is limited by purification. Further, Japanese Patent Laid-Open No. 6-15239 proposes a cleaning method in vacuum using a combustible cleaning agent containing a hydrocarbon as a main component, and a cleaning method using steam generated by heating under reduced pressure and Cleaning devices corresponding to these have been proposed.

[0005]

However, the chlorine-based and chlorofluorocarbon-based solvents such as 1,1,1-trichloroethane and chlorofluorocarbon which have been conventionally used have been used since 1996 when the Montreal Protocol was concluded due to the problem of ozone depletion. There is a problem that it cannot be used. Further, it is pointed out that trichlorethylene and methylene chloride also have a problem of groundwater pollution, and their use is not preferable from the viewpoint of environmental pollution.

On the other hand, the water-based cleaning agent needs to be rinsed after cleaning, which requires a pure water producing apparatus and a waste water treatment apparatus for the cleaning, which causes cost and space problems.
Further, metal parts may have a rust or whitening effect on the surface, or have a problem that they are difficult to dry. Furthermore, the various types of cleaning materials that have been proposed have problems in any of cleaning / drying performance, cost, human safety, and global environmental problems, and are not sufficiently satisfactory.

Further, the detergent containing hydrocarbon as a main component does not have any problem in the above points. In the cleaning using this hydrocarbon, the cleaning agent is heated to improve the cleaning property, a cleaning method in which ultrasonic vibration is applied to remove the dirt, or a dirty cleaning agent is distilled and regenerated. A cleaning method which is also used, and a cleaning method in which a cleaning agent is heated in a reduced-pressure atmosphere to generate steam and steam is used to clean an article in order to improve dryness are often adopted.

As described above, in the cleaning method in which some energy is supplied to the cleaning agent containing a hydrocarbon as a main component, the hydrocarbon containing the main component causes a deterioration reaction such as oxidation, decomposition or polymerization.
There are problems such as deterioration of cleaning property and drying property, generation of irritating odor, coloring of cleaning liquid, and attack on metal parts. Therefore, the above-mentioned Japanese Patent Application Laid-Open Nos. 5-43893 and 6-
Also in the Japanese Patent No. 15239, the same problem occurs because energy is applied to the cleaning agent in the process of ultrasonic cleaning or steam cleaning.

A first object of the present invention is to provide a cleaning composition which does not deteriorate even when the above energy is applied, and a second object thereof is to prevent deterioration. Moreover, it is an object of the present invention to provide a cleaning method capable of exhibiting high cleaning property or drying property.

[0010]

The present invention solves the above-mentioned problems by a detergent composition comprising a hydrocarbon and an alkylmonophenol and a washing method using the same.

Hydrocarbons are relatively stable at room temperature and hardly deteriorate such as oxidation. However, when energy such as heat or ultrasonic waves is applied, carbon-hydrogen bonds are easily broken particularly in isoparaffins, naphthenes, alkylbenzenes, etc., which have a portion represented by the formula (1) in the molecule. , Easily oxidized by oxygen. To prevent this, it is necessary to take measures such as suppressing the heating range to about 100 ° C. or less, cleaning in a state without oxygen, and cleaning without applying ultrasonic waves. However, effective measures cannot be taken due to various constraints such as improvement of cleaning power, complication of equipment, and complication of cleaning process.

The detergent composition comprising a hydrocarbon and an alkyl monophenol of the present invention is a detergent which does not deteriorate. The hydrocarbon used in the present invention has 5 or more carbon atoms and 1
Those of 5 or less are preferable. When the carbon number is less than 5, the flammability is extremely increased, and the safety in handling is poor. On the other hand, when the carbon number is larger than 15, the drying property is extremely slow and it cannot be applied to industrial cleaning.

Alkyl monophenols are usually added in an amount of about 0.01 to 1% to a resin before molding a plastic such as polyethylene, polypropylene, polystyrene, etc. in order to suppress quality deterioration of a molded product.
The addition to a liquid having a very low molecular weight as in the present invention has not been carried out until now, and it is completely novel.

The alkyl monophenols have a molecular structure such that the alkyl free radical formed by breaking the carbon-hydrogen bond of the hydrocarbon by the energy given to the detergent does not bond with oxygen to promote oxidation or deterioration. It acts to scavenge these alkyl radicals by the phenols. Among the hydrocarbons, isoparaffins, naphthenes, and alkylbenzenes, which have a portion represented by the formula (1) in the molecule, tend to be most easily deteriorated. Therefore, it is most effective to combine these hydrocarbons and alkyl monofers. (R ₁ , R ₂ and R ₃ represent an alkyl group and may be the same or different)

The alkyl monophenols of the present invention include 2,6-di-t-butyl-p-cresol and 2,6.
-Di-t-butyl-4-ethylphenol, 2,4,6
-Tri-t-butylphenol, butylated hydroxyanisole, n-octecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,
2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol) and the like can be used. or,
These may be used alone or as a mixture of two or more.

By the way, the substances which are considered to have the action of capturing alkyl free radicals are, for example, 2,2-methylene-bis-, in addition to the above-mentioned alkyl monophenols.
Bisphenol such as (4-methyl-6-t-butylphenol), 1,1,3-tris- (2-methyl-4-)
Polymeric phenols such as hydroxy-5-t-butylphenyl) butane, sulfurized fatty acid esters such as dilaurylthiodipropionate, and phosphoric acid esters such as triphenyl phosphate. However, these cannot be completely dissolved in the detergent composition, the detergent composition is colored, or there is a problem that human safety is poor, and if the melting point and boiling point are too high, the boiling point with hydrocarbon The difference becomes large, and when the cleaning composition is dried, it remains as a dry stain or a dry residue on the surface of the object to be cleaned, which is not preferable.

In the present invention, the alkyl monophenols are added in an amount of 0.001 to 1% by weight based on the main component hydrocarbon. If it is less than 0.001% by weight, the effect of capturing alkyl free radicals is small and the effect of preventing deterioration cannot be maintained. When it is more than 1% by weight, it has a sufficient effect of preventing deterioration, but when the cleaning composition is dried, it is more likely to remain as a dry spot or a dry residue on the surface of the object to be cleaned. Not preferable. From the above,
The addition amount of the alkyl monophenols is optimally the minimum because it is necessary to maintain the performance of the main component hydrocarbon.

A generally commercially available detergent containing hydrocarbon as a main component is used to wash an article to which dirt components such as processing oil, processing waste, grease, wax, flux, pitch and hand grease adhere. In this case, in order to improve the cleaning property, the cleaning agent is often heated or ultrasonic vibration is applied to remove the dirt. These generally commercially available detergents are one kind or a mixture of several kinds selected from isoparaffins, naphthenes and alkylbenzenes.

As described above, such hydrocarbons are deteriorated by breaking the carbon-hydrogen bond due to the energy applied to the cleaning agent, resulting in deterioration of the cleaning property and drying property, generation of irritating odor, coloring of the cleaning liquid, Problems such as attacks on metal parts occur. In the present invention, in order to prevent such deterioration, 2,6-di-t-butyl-p-cresol, 2,6
-Di-t-butyl-4-ethylphenol, 2,4,6
-Tri-t-butylphenol, butylated hydroxyanisole, n-octadecyl-3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate,
2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-
0.001 to 1 of at least one kind of alkyl monophenol selected from ethyl-6-t-butylphenol)
% By weight.

As a result, the cleaning agent does not deteriorate except for the dirt components brought into it, so that the performance of the cleaning agent composition can be maintained for a long period of time and its life can be easily grasped. After this, the cleaning composition may be dried immediately, or may be washed again with the cleaning composition and then dried. Alternatively, it may be dried after being replaced with a detergent that is easier to dry than the detergent composition.

[0021] The cleaning agent containing hydrocarbon as a main component may be regenerated and reused after being contaminated due to contamination. As a regeneration method, a method is generally used in which the detergent is heated to a boiling point or higher under normal pressure or reduced pressure and distilled. Since energy is applied for heating in this manner, the carbon-hydrogen bond of the hydrocarbon is broken and deteriorates.
This tendency is more remarkable as the distillation temperature is higher or the reduced pressure is lower.

In order to prevent such deterioration, 2,6-di-t-butyl-p-cresol, 2,
6-di-t-butyl-4-ethylphenol, 2,4
6-tri-t-butylphenol, butylated hydroxyanisole, n-octadecyl-3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate,
2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-
0.001 to at least one alkyl monophenol selected from ethyl-6-t-butylphenol)
1% by weight is added. As a result, the performance of the cleaning agent can be maintained for a long time because the cleaning agent does not deteriorate, and the amount of cleaning agent used can be minimized.

According to the cleaning method of the present invention, the 95% distillation temperature is within 5 ° C. from the initial boiling point and the 99% distillation temperature is the initial boiling point of the article to which the dirt component or the detergent in the previous step is attached. To 10 ° C. from the distillation of isoparaffin having 8 to 12 carbon atoms and 2,6-di-t-butyl-p
-Cresol, 2,6-di-t-butyl-4-ethylphenol, 2,4,6-tri-t-butylphenol,
Butylated hydroxyanisole, n-octadecyl-3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis- (4
-Methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol) from 0.001 to 1% by weight of at least one alkyl monophenol selected from After cleaning with the cleaning composition, the cleaning composition is dried and finished.

The method for measuring the distillation property and the meaning of the terms are defined in JIS K2254. When 100 ml of isoparaffin is heated at a heating rate such that the average amount of distillate is 5 ml / min, The temperature at which one drop of is distilled is the initial distillation point, the temperature at which 95 ml is distilled is the 95% distillation temperature, and the temperature at which 99 ml is distilled is the 99% distillation temperature.

Normally, when vaporizing and removing the cleaning liquid adhering to the object to be cleaned, the film of the cleaning liquid adhering to the object to be cleaned will be uniform if all the naturalization rates of all components of the cleaning liquid are the same. It becomes thin and vaporizes at the end, and it can be finished in high quality without spots. However, when the rate of vaporization of all the components of the cleaning liquid is different, the components that are easily vaporized are vaporized first, and the components that are difficult to vaporize are left in an island shape and are not dried uniformly. Then, dust and the like are aggregated on the island-shaped remaining portion, so that stains occur and high quality finishing cannot be achieved.

Therefore, in the detergent composition used immediately before the drying step, it is necessary to control the distillation property that controls the rate of vaporization, that is, the temperature range of the distillation temperature. As a result of examination by the present inventor, the distillation property is such that the 95% distillation temperature is within 5 ° C. from the initial distillation point and the 99% distillation temperature is within 10 ° C. from the initial distillation point, and the carbon number is 8 or more and 12 or less. It became clear that high-purity isoparaffin was necessary.
When the temperature is wider than this temperature range, many components are difficult to vaporize and the composition is not dried uniformly, so that stains are generated on the surface of the object to be cleaned and high quality cannot be finished. Further, if the carbon number is less than 8, the flammability increases and the handling safety decreases, which is not preferable. On the contrary, when the carbon number is more than 12, the drying speed is slow and it becomes difficult to dry, which is not preferable.

For the same reason as above, the addition amount of the alkyl monophenols should be 0.001 to 1% by weight. If it is less than 0.001% by weight, the effect of capturing alkyl free radicals is small and the effect of addition cannot be sustained. If it is more than 1% by weight, the effect of addition is
When the cleaning composition is dried, there is a high possibility that it will remain as simple stains or dry residues on the surface of the object to be cleaned, which is not preferable. For this reason, the addition amount of alkyl monophenols is optimally the minimum necessary to maintain the performance of the main component hydrocarbon. Further, high molecular weight phenols, sulfurized fatty acid esters and phosphoric acid esters which are considered to have similar effects have a large difference in boiling point from isoparaffin, which is not preferable.

The present invention is to regenerate and reuse a detergent composition consisting of isoparaffin and alkyl monophenols which have been soiled by soil components or the detergent used in the previous step. In particular, in the cleaning method of drying and finishing the detergent composition as it is, as described above, it is necessary to control the distillation property that governs the rate of vaporization, that is, the temperature range of the distillation temperature, and the mixing of substances with different boiling point differences. Must be suppressed as much as possible. Therefore, the regeneration of the detergent composition is an important step.

As such a regeneration method, a method is generally used in which the detergent is heated to a boiling point or higher under normal pressure or reduced pressure and distilled. Since energy is applied for heating in this manner, the carbon-hydrogen bond of the hydrocarbon is broken and deteriorates. Particularly in isoparaffin, the carbon-hydrogen bond is easily broken. Further, the higher the distillation temperature or the lower the degree of reduced pressure, the more remarkable the deterioration progresses. In order to prevent such deterioration, in the present invention, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,4,6-tri-t-butylphenol. , Butylated hydroxyanisole, n-octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol)
0.001 to 1% by weight of at least one alkyl monophenol selected from the above is added. As a result, since it does not deteriorate, the performance of the cleaning composition can be maintained for a long time,
The amount used can be minimized.

The steam cleaning is a cleaning method that has been widely performed when the object to be cleaned has a complicated shape or when it is desired to remove dirt with high quality in a short time. Since it is dangerous to use an open system with a flammable cleaning agent, use a closed system for cleaning while reducing the risk of ignition. First, the material to be cleaned is loaded into the airtight container and depressurized to a certain pressure, the 95% distillation temperature is within 5 ° C from the initial distillation point, and the 99% distillation temperature is 10 ° C from the initial distillation point.
The cleaning agent composition consisting of isoparaffin and alkylphenol having a distillation property, which is within the range, is heated to generate steam to remove the cleaning agent or dirt component in the previous step adhering to the object to be cleaned. Then, after a certain period of time, the inside of the container is returned to atmospheric pressure to finish the object to be cleaned. In this cleaning method, the cleaning agent composition is required to finish the object to be cleaned with high quality and to perform stable steam supply without change in the steam supply amount over time.

As a result of a study conducted by the present inventors, the distillation property has a carbon number of 8 or more 12 with a 95% distillation temperature within 5 ° C. from the initial boiling point and a 99% distillation temperature within 10 ° C. from the initial boiling point. It became clear that it is necessary to have high-purity isoparaffin that is: If the temperature range is wider than the above temperature range, many components are difficult to vaporize, and since the components are not uniformly dried, stains are generated on the surface of the object to be cleaned, and high quality finishing cannot be achieved. Further, if the carbon number is less than 8, the flammability is extremely increased and the handling safety is lowered, which is not preferable. On the contrary, when the carbon number is more than 12, the drying speed is extremely slow and it is difficult to dry, which is not preferable.

Further, for the same reason as above, the addition amount of the alkyl monophenols needs to be 0.001 to 1% by weight. If it is less than 0.001% by weight, the effect of capturing alkyl free radicals is small and the effect of addition cannot be sustained. Further, if it is more than 1% by weight, it has the effect of addition, but it is not preferable because the possibility that it will remain as a dry spot or a dry residue on the surface of the object to be cleaned when the cleaning composition is dried. The addition amount of alkyl monophenols is optimally the minimum necessary to maintain the performance of isoparaffin. High molecular weight phenols, sulfurized fatty acid esters and phosphoric acid esters which are thought to have similar effects are not preferable because of a large difference in boiling point from isoparaffin.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION

(Embodiment 1) <Cleaning composition> First tank Naphthesol M 99.9% by weight (Nippon Oil Co., Ltd., naphthenes having 11 to 13 carbon atoms) 2,6-di-t-butyl-p -Cresol 0.1 wt% 2nd tank isononane 99.999 wt% (95% distillation temperature is 4 ° C from the initial boiling point and 99% distillation temperature is 5 ° C from the initial boiling point C9 Isoparaffins) 2,6-di-t-butyl-p-cresol 0.001% by weight <Item to be washed> Aluminum tape recorder parts (6 blind holes of about 60 x 100 mm, diameter φ4, depth 6 mm) <Dirt> Water-insoluble cutting oil (Dafney Cleaner HS-5, manufactured by Idemitsu Kosan Co., Ltd.) <Cleaning method> 20 pieces of the above parts are placed vertically in the yatoy, and the cleaning line consists of 2 tanks shown in FIG. Washed.
Then, it was dried in a drying oven which was sprayed with a temperature of 80 ° C. which was cleaned with a HEPA filter. This operation was repeated 5 times to wash a total of 100 parts.

<Evaluation method> Ultrasonic vibration (27 kH) for 4 hours
(z600W) was continuously added to the detergent composition, and the composition change was confirmed by gas chromatography. The presence or absence of cutting scraps and cutting oil residues (stains) is checked with a microscope (10
Double) to confirm the washability and dryness.

In this embodiment, as the cleaning agent for the first tank,
99.9% by weight of Naphthesol M containing naphthenes having 11 to 13 carbon atoms as main components, and 0.1% of 2,6-di-t-butyl-p-cresol which is alkylmonophenol.
Using a detergent composition composed of 1% by weight, dimethylheptane having a 95% distillation temperature of 4 ° C from the initial boiling point and a 99% distillation temperature of 5 ° C from the initial boiling point is mainly used as the cleaning agent in the second tank. A detergent composition comprising 99.999% by weight of isononane as a component and 0.001% by weight of 2,6-di-t-butyl-p-cresol which is an alkyl monophenol is used.

Prior to cleaning the parts, first and second
Ultrasonic vibration (27 kHz, 600 W) was continuously added in the tank for 4 hours, and each cleaning composition was sampled to confirm the deterioration state, and the composition change was confirmed by gas chromatography. The above parts were subsequently washed. In the 1st and 2nd tanks, ultrasonic vibration (27kHz60
0 W) was added to wash.

From the measurement by gas chromatography, it was found that a new peak of the deterioration product was not confirmed and the product was stable and did not deteriorate. Furthermore, the number of washed sheets is 100 even under microscope observation.
It was found that the number of defective products was 1 and the cleaning and drying properties were excellent.

As described above, the detergent composition comprising the hydrocarbon of naphthenes or isoparaffins and the alkyl monophenols is excellent in detergency and drying property and imparts energy such as ultrasonic vibration. Is stable for a long time and does not deteriorate.

(Embodiment 2) <Cleaning composition> First tank isododecane 99.99% by weight (95% distillation temperature is 5 ° C. from the initial boiling point, and 99% distillation temperature is from the initial boiling point) 7 ° C. Isoparaffins having 12 carbon atoms) 2,4,6-tri-t-butylphenol 0.01 wt% <Cleaned> Cutting oil Unicut GH-35 (manufactured by Nippon Oil Co., Ltd.) <Cleaning method> The above-mentioned detergent composition was put into the first and second tanks of the cleaning line consisting of the two cleaning tanks and the distillation apparatus shown in FIG. The detergent composition overflowed from the second tank is adapted to enter the first tank. And the first
The detergent composition overflowed from the tank was introduced into a distillation apparatus and was regenerated by distillation. The regenerated cleaning composition was returned to the second tank. The cleaning composition over-followed from the second tank was returned to the first tank and the cleaning composition in the first tank was cleaned. This operation was continued for 4 hours.

<Evaluation Method> The deteriorated state of the cleaning compositions in the first and second tanks was sampled after 4 hours and the composition change was confirmed by gas chromatography.

In the present embodiment, 99.99% by weight of isododecane, which is an isoparaffin having 12 carbon atoms, and 2,4,6-tri-t-, which is an alkylmonophenol, are used as the cleaning agents for the first and second tanks. A detergent composition consisting of 0.01% by weight of butylphenol is washed while being regenerated by distillation. Assuming that the amount of the dirt component brought into the first tank was 5% by weight, 5% by weight of cutting oil was mixed to obtain a dirty detergent composition. The dirty detergent composition overflowing from the first tank was introduced into a distillation apparatus and regenerated under reduced pressure. The distillation conditions are a vacuum degree of 40 mmHg and a distillation temperature of 120 ° C.

As a result of the evaluation, in the composition analysis of the cleaning composition after 4 hours by gas chromatography, new products due to deterioration in the cleaning compositions in the first and second tanks were found before and after the distillation. I could not confirm. Thus, it can be seen that the detergent composition containing the alkyl monophenols is stable for a long time and does not deteriorate even when heated. (Embodiment 3) <Cleaning composition> First tank Cleansol G 99% by weight (Nippon Oil Co., Ltd., alkylbenzenes) Butylated hydroxyanisole 1% by weight Second tank isononane (95% distillation temperature Is 4 ° C. from the initial boiling point and 99.999% by weight 99% Distillation temperature is 5 ° C. from the initial boiling point) Butylated hydroxyanisole 0.001% by weight X 200 mm) <Dirt> Press oil <Cleaning method> Ten parts were placed vertically in a yatto and washed in a cleaning line consisting of a cleaning tank and a steam cleaning tank shown in FIG. This operation was repeated 20 times.

<Evaluation method> The presence or absence of a residue (stain) of the press oil was visually observed to confirm the cleaning property and the drying property. Also,
After the deterioration state of the detergent composition in the second tank was completed 20 times (after about 3 hours), the composition was collected by gas chromatography and the change in composition was confirmed.

The present embodiment is a detergent composition comprising 99% by weight of alkylbenzenes Clean Sol G having 12 to 13 carbon atoms as a main component and 1% by weight of butylated hydroxyanisole which is an alkylmonophenol. The first
As a cleaning agent for the second tank, a cleaning agent composition comprising 99.999% by weight of isononane, which is an isoparaffin having 9 carbon atoms, and 0.001% by weight of butylated hydroxyanisole, which is an alkylmonophenol, is used as the cleaning agent for the second tank. The second tank was used for steam cleaning under reduced pressure. In the first tank, ultrasonic vibration was added for cleaning to improve the cleaning power. In the second tank, the steps of charging the object to be cleaned, depressurizing the airtight cleaning tank, introducing steam of the cleaning agent, vacuum drying, leaking, and taking out the object to be cleaned were performed. The cleaning agent vapor was generated at a vacuum degree of 100 mmHg and a cleaning agent distillation temperature of 120 ° C.

As a result of the evaluation, the number of defective products was 5 out of 200 washed sheets, and there was no change in washing property and drying property.
Further, in the composition analysis by gas chromatography, no new product due to the deterioration of the cleaning composition in the second tank was confirmed before and after the cleaning. As mentioned above,
It can be seen that the detergent composition containing the alkyl monophenols is stable for a long time and does not deteriorate even when heated. (Comparative Example 1) <Comparative Example 1> First tank Naphthesol M 100% by weight (Nippon Oil Co., Ltd., naphthenes having 11 to 13 carbon atoms) Second tank Isononane 100% by weight (95% distillation temperature is the first 4 ° C. from the boiling point and 99% distillation temperature from the initial boiling point to 5 ° C.) <Subject to be cleaned> Same as Embodiment 1 <Dirt> Same as Embodiment 1 <Cleaning method> Embodiment Same as 1. <Evaluation method> Same as in the first embodiment

In this comparative example, cleaning is performed with the cleaning composition obtained by removing the alkyl monophenol 2,6-di-t-butyl-p-cresol from the composition of the first embodiment and the cleaning composition.

From the measurement by gas chromatography, the first
Also, many new products due to deterioration could be confirmed in any of the cleaning compositions in the second tank. In addition, microscopic observation revealed that there were 64 flow-like spots, which were considered to be due to the liquid remaining in the 200 washed sheets, and were defective.

As described above, when the alkyl monophenols are not added, the detergent composition deteriorates due to ultrasonic vibration or heating and the initial performance cannot be maintained for a long time. (Comparative Example 2) First tank and second tank isododecane 100% by weight (95% distillation temperature is 5 ° C from the initial boiling point and 99% distillation temperature is 7 ° C from the initial boiling point, and has 12 carbon atoms. Isoparaffins) <Dirt> Same as the second embodiment <Cleaning method> Same as the second embodiment <Evaluation method> Same as the second embodiment

In this comparative example, the alkyl monophenol 2,6-di-t-butylphenol from the detergent composition of the second embodiment is introduced into a distillation apparatus and regenerated under reduced pressure.

As a result of the evaluation, a large number of new products due to deterioration were confirmed in the composition of the detergent composition after 4 hours by gas chromatography in both the detergent compositions of the first and second tanks.

As described above, it can be seen that the detergent composition containing no alkyl monophenols is unstable and deteriorates at a high temperature of 120 ° C. and cannot be used while being regenerated by distillation for a long time.

(Comparative Example 3) First tank Clean Sol G 100% by weight (Nippon Oil Co., Ltd., alkylbenzenes) Second tank Isononane 100% by weight (95% distillation temperature is 4 ° C from the initial distillation point, And the 99% distillation temperature is 5 ° C. from the initial boiling point) <Dirt> Same as the third embodiment <Cleaning method> Same as the third embodiment <Evaluation method> Same as the third embodiment

In this comparative example, cleaning was performed with the cleaning composition obtained by removing the alkyl monophenol butylated hydroxyanisole from the cleaning composition of the third embodiment.

As a result of the evaluation, there were 64 flow-like stains which were considered to be caused by the liquid remaining in the 200 washed sheets, which was a defective product. Also, in the composition analysis by gas chromatography, many new products due to deterioration were confirmed in both the cleaning composition in the first tank and in the cleaning composition before and after the completion of cleaning after 3 hours.

As described above, when the alkyl monophenols are not added, it becomes unstable and deteriorates due to ultrasonic vibration or heating and cannot be used for a long period of time.

[0056]

INDUSTRIAL APPLICABILITY As described above, the present invention maintains the advantages such as excellent cleaning / drying property, cost, human safety and global environment protection of the detergent composition mainly containing hydrocarbon for a long period of time. Therefore, the article can be finished with stable quality and the running cost can be kept low. Further, since a chlorine-based solvent such as CFC is not used, there is no fear of ozone layer destruction, and it is safe for the human body to remove multi-layer stains.

[Brief description of drawings]

FIG. 1 is a block diagram of a cleaning device that performs cleaning in Embodiment 1 and Comparative Example 1.

FIG. 2 is a block diagram of a cleaning device that performs cleaning in Embodiment 2 and Comparative Example 2.

FIG. 3 is a block diagram of a cleaning device that performs cleaning in Embodiment 3 and Comparative Example 3.

Claims (9)

[Claims] 1. A detergent composition comprising a hydrocarbon having 5 to 15 carbon atoms and 0.001 to 1% by weight of an alkyl monophenol. 2. The hydrocarbon is one kind or a mixture of several kinds selected from isoparaffins, naphthenes and alkylbenzenes having a moiety represented by the formula (1) in the molecule. Claim 1
The cleaning composition according to the above. (R ₁ , R ₂ and R ₃ represent an alkyl group and may be the same or different) 3. The hydrocarbon has a 95% distillation temperature within 5 ° C. from the initial distillation point and a 99% distillation temperature within 10 ° C. from the initial distillation point.
The cleaning composition according to claim 1, which is an isoparaffin having a carbon number of 8 or more and 12 or less and having a distillation property of not higher than 0 ° C. 4. The alkyl monophenols are 2,6
-Di-t-butyl-p-cresol, 2,6-di-t-
Butyl-4-ethylphenol, 2,4,6-tri-t
-Butylphenol, butylated hydroxyanisole,
n-octadecyl-3- (3,5-di-t-butyl-4
-Hydroxyphenyl) propionate, 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-methyl-6-
The cleaning composition according to any one of claims 1 to 3, which is at least one alkyl monophenol selected from t-butylphenol). 5. A detergent composition containing hydrocarbon as a main component is added to 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,4. 6-tri-t-butylphenol, butylated hydroxyanisole, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propinate, 2,2 '
-Methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl-)
At least 1 selected from 6-t-butylphenol)
0.001 to 1% by weight of seed alkyl monophenols
A cleaning method comprising adding and cleaning an article. 6. The cleaning method according to claim 5, wherein the cleaning composition to which the alkyl monophenols have been added is regenerated by distillation and returned to the original state. 7. An isoparaffin having a carbon number of from 8 to 12 and 2, which has a distillation property and has a 95% distillation temperature within 5 ° C. from the initial boiling point and a 99% distillation temperature within 10 ° C. from the initial boiling point. 6-di-t-butyl-p-cresol, 2,6-
Di-t-butyl-4-ethylphenol, 2,4,6-
Tri-t-butylphenol, butylated hydroxyanisole, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,
At least one alkyl monophenol selected from 2'-methylene-bis- (4-methyl-6-t-butylphenol) and 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol). A cleaning method, comprising: washing an article with a cleaning composition comprising 0.001 to 1% by weight, and then drying and finishing the cleaning composition. 8. The cleaning method according to claim 7, wherein the cleaning composition is regenerated by distillation and returned to the original state. 9. An isoparaffin having a carbon number of 8 or more and 12 or less, which has a distillation property and has a 95% distillation temperature within 5 ° C. from the initial boiling point and a 99% distillation temperature within 10 ° C. from the initial boiling point, and 2. 6-di-t-butyl-p-cresol, 2,6-
Di-t-butyl-4-ethylphenol, 2,4,6-
Tri-t-butylphenol, butylated hydroxyanisole, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,
At least one alkyl monophenol selected from 2'-methylene-bis- (4-methyl-6-t-butylphenol) and 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol). A cleaning method comprising heating 0.001 to 1% by weight of a cleaning composition in a reduced pressure atmosphere to generate steam, and cleaning the article with the steam.