JP2015040217A - Detergent composition and distillation reproduction system therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition which exhibits excellent washing performance for both of an oily processing oil and a water-soluble processing oil, causes no stains and can be reproduced without gravity separation, and to provide a distillation reproduction system for such a detergent composition.SOLUTION: There is provided substantially 100 vol% of a detergent composition which is obtained by incorporating 50 to 1.0 vol% in total of a surfactant and water into 50 to 99 vol% of a base solvent obtained by adding a glycol ether-based solvent to a naphthene-based hydrocarbon solvent composed mainly of naphthene, wherein the surfactant has an HLB of 10 to 14.

Description

  The present invention relates to a cleaning composition that exhibits excellent cleaning performance for both oil-based processing oil and water-soluble processing oil, and a distillation regeneration system thereof.

  The hydrocarbon solvent is generally classified into normal paraffin type, isoparaffin type, naphthene type, and aromatic type, and all have the advantage that they are less corrosive to metals and can be regenerated by distillation. Naphthenic solvents have higher detergency than paraffinic solvents and are suitable for degreasing cleaning of metal parts such as iron, copper, aluminum, and stainless steel.

JP 2007-283191 A JP 2010-174106 A

  By the way, recently, metal processing using a water-soluble processing oil is increasing, and therefore a one-part cleaning agent that can handle not only oil-based processing oil but also water-soluble processing oil is desired.

  However, when a processed product processed with a water-soluble processing oil is washed with a hydrocarbon-based solvent, stains (solid residue of water-soluble processing oil) are generated after washing, and in particular, a water-soluble processing oil in a dry state. There is a problem that stains are unavoidable for a processed product to which no matter is attached, no matter how a hydrocarbon solvent having excellent detergency is used.

  In view of this point, a cleaning agent that prevents the occurrence of stains has been proposed (Patent Document 1 and Patent Document 2), but any of the inventions has significant problems in cleaning performance and regeneration processing.

  For example, since the cleaning agent described in Patent Document 1 is premised on specific gravity separation, there is a problem in that the liquid composition lacks homogeneity in the cleaning tank and thus there is a local difference in cleaning performance. On the other hand, the cleaning agent of Patent Document 2 is a W / O emulsion type, and after the cleaning process, the working time of 8 hours is required for the layer separation due to the specific gravity difference between the water layer containing the water-soluble processing oil and the hydrocarbon solvent layer. (Paragraph 0037).

  The present invention has been made in view of the above-mentioned problems. In addition to exhibiting excellent cleaning performance for both oil-based processing oil and water-soluble processing oil, there is no occurrence of spots, and specific gravity It is an object of the present invention to provide a detergent composition that can be regenerated without undergoing separation, and a distillation regeneration system for such a detergent composition.

  In order to achieve the above object, the detergent composition according to the present invention comprises a surfactant and a base solvent of 50 to 99 Vol% obtained by adding a glycol ether solvent to a naphthene hydrocarbon solvent containing naphthene as a main component. The cleaning composition is substantially 100 Vol% by containing 50 to 1.0 Vol% of water as a whole, wherein the surfactant has an HLB of 10 to 14. In addition, in this specification, the numerical range shown by-is the concept containing the numerical value of both ends.

  The present invention is substantially composed of a base solvent, a surfactant and water, but it is sufficient that the total amount is substantially 100 Vol%, and one or more additives of about 10 to 100 ppm. The addition of is not prohibited. As the additive, for example, an antioxidant of about 50 ppm can be exemplified.

  In the present invention, since a glycol ether solvent is added to a naphthenic hydrocarbon solvent having excellent detergency, it is possible to wash heavy and high-viscosity oily soil that cannot be removed by a hydrocarbon solvent alone due to the high solubility of glycol. can do. For example, the flux residue adhering when solder is used can be reliably removed.

  Here, ethylene glycols, diethylene glycols, propylene glycols, dipropylene glycols, triethylene glycols and the like are used alone or in combination as the glycol ether solvent. Among these, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether, propylene glycol methyl ether acetate Dipropylene glycols including dipropylene glycol methyl ether acetate, propylene glycol diacetate, propylene glycol diacetate, dipropylene glycol dimethyl ether and the like are preferably selected, and dipropylene glycol dimethyl ether acetate is particularly preferably used.

  In any case, the boiling point of the naphthenic hydrocarbon solvent and the glycol ether solvent is preferably 200 to 220 ° C. under normal pressure. A high-purity base solvent can be regenerated by distillation.

  Here, the contained Vol ratio of the naphthene hydrocarbon solvent and the glycol ether solvent is preferably 6: 1 to 1: 1, more preferably 5: 1 to 3: 1 and even more preferably 4 Should be ± 0.4: 1.

  In the present invention, the surface active HLB is 10 to 14, and if it exceeds this range, phase separation occurs and a transparent cleaning agent cannot be obtained. HLB is calculated by the Griffin equation.

  The surface activity of the present invention is not particularly limited as long as the HLB is 10 to 14, but a nonionic surfactant is preferably selected. As the nonionic surfactant, an alkylphenol type surfactant such as polyoxyalkylene alkylphenol ether or a higher alcohol type surfactant such as polyoxyethylene polyoxypropylene alkyl ether is preferably selected, and more preferably a higher alcohol type. Are selected.

The higher alcohol surfactant is not limited to ethylene oxide single addition type (POE type), and ethylene oxide and propylene oxide addition type (PPO-POE type) are also preferably selected. Further, the higher alcohol having 10 to 15 carbon atoms is preferably selected, and as a preferable surfactant, for example, molecular formula RO (CH ₂ CH ₂ O) _n (CH ₂ CH (CH ₃ ) O) _m H or , RO (CH ₂ CH ₂ O) _n (CH ₂ CH ₂ CH ₂ O) _m H, polyoxyethylene polyoxypropylene alkyl ether represented by H, and polyoxyethylene tridecyl ether C ₁₃ H ₁₇ O (CH ₂ CH ₂ O) _n H and the like, all of which have an HLB of 10 to 14.

  In any case, when the surfactant is a monomeric type of one hydrophobic chain and one hydrophilic group type, the content of the surfactant is 50 Vol% or more, preferably with respect to the total amount of the surfactant and water. It is preferable to set to 53-80 Vol%. Here, when water is contained exceeding 50 Vol%, even if the surfactant of HLB 10-14 is used, phase separation between water and the solvent occurs and the homogeneous cleaning performance is hindered.

  On the other hand, when the surfactant is a gemini type formed by binding a surfactant having one hydrophobic chain and one hydrophilic group with a spacer, the surfactant is contained in the total amount Vol of the surfactant and water. The content can be greatly reduced. In this case, the water content Vol can be set to 50 to 90 Vol% with respect to the total amount Vol of the surfactant and water, and the amount of the surfactant used can be greatly increased with respect to the required amount of water. Can be suppressed. That is, the surfactant content can be 50 to 10 Vol% with respect to the total amount Vol of the surfactant and water.

  Therefore, even when the base solvent is regenerated by distillation, the amount of surfactant discarded can be reduced. Further, since the gemini type can relatively increase the amount of water compared to the case of the monomeric type, it is possible to constitute a non-flammable cleaning composition.

  By the way, the cleaning agent of the present invention is preferably processed by a predetermined distillation system so that the base solvent is concentrated and regenerated, and a necessary amount of a surfactant and water are replenished as a cleaning agent. Reused.

  Here, the distillation system includes a reboiler that receives the used cleaning agent, a distillation column that receives the vapor from the reboiler, and a reflux that is configured to receive a distillate from the distillation column and return it to the distillation column. It is preferable to have a tank and an intermediate tank configured to receive the bottoms from the distillation tower and return it to the reboiler.

  In addition, the used cleaning agent is continuously used while removing foreign substances and circulating between the immersion cleaning tank and the reserve tank, while a part of the cleaning agent in the reserve tank is regularly supplied to the distillation system. It is preferably configured to be supplied and regenerated.

  Moreover, the throughput of the distillation system is 50 to 300 liters per time, and after the distillation process for 0.5 to 3 hours, each concentrated regenerated solution in the reflux tank and the intermediate tank is replenished with the necessary constituent composition. In addition, it is preferably configured to be supplied to a reserve tank or to be stored in an adjustment tank connected to an immersion cleaning tank.

  The present invention also relates to a reboiler that receives a cleaning agent after use, a distillation column that receives steam from the reboiler, and a reflux tank that is configured to receive a distillate from the distillation column and return it to the distillation column. And an intermediate tank configured to receive the bottoms from the distillation column and recirculate it to the reboiler.

  As described above, the cleaning composition according to the present invention exhibits excellent cleaning performance for both oil-based processing oil and water-soluble processing oil, is free from spots, and undergoes specific gravity separation. It is possible to reproduce without. Moreover, the distillation regeneration system according to the present invention can regenerate the cleaning composition exhibiting the above-described effects with high efficiency.

1 illustrates an example of a cleaning system including a multi-effect batch distillation system. 1 is a more detailed view of a multi-effect batch distillation system. It is drawing which shows the modification of FIG.

  Hereinafter, although an Example is described, the concrete description content does not limit this invention at all.

<Solubility test>
The total amount of polyoxyethylene tridecyl ether (Neugen TDS: Daiichi Kogyo Seiyaku Co., Ltd.) and water is added to 25 to 10 Vol% to a base solvent 75 to 90 Vol% constituted by adding a glycol ether solvent to a naphthene hydrocarbon solvent. The solubility was confirmed by changing the blending ratio of water and the surfactant. In addition, it experimented about Neugen TDS of each grade (HLB: 8.0-16.3) from which HLB differs.

  In addition, for the same type of higher alcohol ether type nonionic surfactant (polyoxyethylene polyoxypropylene alkyl ether), the HLB, the content ratio of the base solvent, and the mixing ratio of water and the surfactant are appropriately changed. The solubility of the detergent was confirmed.

  As a result, it has been found that a surfactant having HLB of 10 to 14 (more preferably, HLB of 12 to 13.5) is suitable. In addition, it was confirmed that phase separation occurred when the surfactant content relative to the total amount of the surfactant and water was less than 50 Vol%, not limited to the type of surfactant. Since phase separation also occurs inside the cleaning tank, there is a local variation in cleaning performance. On the other hand, if the content of the surfactant with respect to the total amount of the surfactant and water is set to 50 Vol% or more (depending on the surfactant, 55 Vol% or more), it becomes a transparent cleaning agent and is homogeneous in place. Cleaning performance is guaranteed.

  In addition, when a laboratory-level gemini surfactant was obtained and a similar experiment was conducted, it was confirmed that the same solubility was exhibited with a use amount of about 1/10 of a commercially available surfactant.

  The above-mentioned tendency is common regardless of the content ratio of the surfactant and water, and the base solvent. However, when the content ratio of the base solvent is decreased to less than 50 Vol%, the cleaning performance deteriorates. The content ratio of the naphthene hydrocarbon solvent and the glycol ether solvent is preferably 6: 1 to 1: 1, more preferably 5: 1 to 3: 1. Confirmed by experiment. Moreover, all the boiling points of each solvent are about 200-210 degreeC.

<Cleaning performance test>
10 vol% of HLB 10.5 surfactant (Neugen TDS-50: Daiichi Kogyo Seiyaku Co., Ltd.) and 5.0 vol% of water are prepared in the base solvent 85 vol% to obtain the cleaning agent of the example. The cleaning performance for processing oil was tested.

  As the oil-based processing oil, low-viscosity Aquapress F-85 (Aqua Chemical) and medium-viscosity Aqua Press L-107A (Aqua Chemical) were used. Moreover, as a water-soluble processing oil, Hisol X (Beep Japan) was used.

  Each test piece (SUS304) was immersed in these processing oils for 30 minutes, drained, and the water-soluble processing oil was further dried in a 60 ° C. environment for 30 minutes.

  For the three types of test pieces to which processing oil is attached in this way, the first ultrasonic cleaning (4 minutes) ⇒ the second ultrasonic cleaning (reduction pressure 5 times, 4 minutes) ⇒ steam cleaning (2 Min) => vacuum drying (160 seconds) was performed.

  As the cleaning liquid, an isoparaffin-based hydrocarbon solvent (solvent GF: Aqua Chemical), which is Comparative Example 1, and a glycol ether-based solvent (AQ # 200: Aqua Chemical), which is Comparative Example 2, are used. Cleaning performance was compared using cleaning agents.

  As a result, the test piece to which the oil-based processing oil was adhered was confirmed to have the same level of cleaning performance regardless of the viscosity of the processing oil, regardless of which cleaning agent was used. In other words, it was confirmed that the cleaning agents of the examples exhibited cleaning performance comparable to that of non-aqueous hydrocarbon solvents.

  On the other hand, about the test piece to which water-soluble processing oil was made to adhere, when this was wash | cleaned with the cleaning agent of the comparative example 1 or the comparative example 2, the visible spot was confirmed. On the other hand, in the case of cleaning with the cleaning agent of the example, all the test pieces were reliably cleaned, and no generation of spots was observed.

<Distillation regeneration system>
The cleaning agents of the examples are regenerated and reused in a multi-effect batch distillation system SYS. FIG. 1 illustrates an example of a cleaning system including a multi-effect batch distillation system SYS, using a first ultrasonic cleaning tank 1 that uses the semi-aqueous cleaning agent of the embodiment and a non-aqueous cleaning agent. A second ultrasonic cleaning tank 2 and a steam cleaning tank 3 are shown.

  The metal processed product to which oil-based processing oil or water-soluble processing oil is attached is transferred in the order of first ultrasonic cleaning tank 1 ⇒ second ultrasonic cleaning tank 2 ⇒ steam cleaning tank 3 and finished in the steam cleaning tank 3. The rinsing process and the vacuum drying process are completed. In this case, since the cleaning agent of the example is used in the first ultrasonic cleaning tank 1, even if the metal processed product is attached with water-soluble processing oil, a stain is generated on the metal processed product after the cleaning process is completed. There is no.

  As the non-aqueous cleaning agent used in the second ultrasonic cleaning tank 2, the base solvent of the example is preferably used. Since the base solvents of the examples have the same boiling point between the naphthenic hydrocarbon solvent and the glycol ether solvent, they are distilled and regenerated in the distillation regeneration tank 6 and reused in the second ultrasonic cleaning tank 2 and the steam cleaning tank 3. The The steam cleaning tank 3 and the distillation regeneration tank are appropriately depressurized by a vacuum pump. Moreover, about the 2nd ultrasonic cleaning tank 2, pressure reduction and a return pressure can be repeated.

  By the way, the cleaning agent of the embodiment circulates in the route of the first ultrasonic cleaning tank 1 ⇒ the reserve tank 4 ⇒ the circulation pump P ⇒ foreign matter removal filter F ⇒ the first ultrasonic cleaning tank 1 and batch-processes the distillation system. It is supplied to SYS and concentrated and separated into three components: a base solvent, water, and a surfactant. The whole amount of the surfactant concentrate is discarded, while the base solvent and water are reused in the first ultrasonic cleaning tank 1.

  Therefore, not only does it become unnecessary to discard the dirty base solvent and water, but the degree of contamination of the cleaning agent in the first ultrasonic cleaning tank 1 can always be kept below a predetermined level.

  FIG. 2 is a diagram showing the multi-effect batch distillation system SYS in more detail. As illustrated, the distillation regeneration system SYS passes through a reboiler 10 that receives the used cleaning agent from the reserve tank 4, a distillation column 11 that receives steam from the reboiler 10, and a condenser 17 that is maintained at about 20 ° C. A distillate from the distillation column 11 was received, and a reflux tank 12 configured to be able to be refluxed to the distillation column 11 and a bottoms from the distillation column 11 were received and configured to be refluxed to the reboiler 10. The middle tank 13 is mainly configured. Then, the distillation column 11 is regularly operated at total reflux.

  This distillation system SYS is a three-component system composed of water having a boiling point of 100 ° C., a mixed solvent having a boiling point of about 200 ° C., and a surfactant, and is designed as a three-stage distillation column with the reboiler 10 and the distillation column 11. . Further, a distillation column designed at 100 to 150 ° C. and 0.1 atm is configured by connecting the vacuum pump 16 to the reflux tank 12.

  The liquid introduced into the reboiler 10 (cleaning deterioration liquid) is heated by the heat medium oil stored in the heated oil tank 14, and the concentrated liquid in the reboiler 10 is configured to be transferred to the drain tank 19. Accordingly, the entire amount of the surfactant is discarded together with the processing oil removed and separated from the metal processed product.

  An oil expansion tank TN1 is connected to the oil tank 14 to receive the heat medium oil that has been thermally expanded. A heat exchanger 15 is connected to the intermediate tank 13.

  The water collected in the reflux tank 12 and the mixed solvent collected in the intermediate tank 13 are cooled to the room temperature level by the total reflux operation for a predetermined time, and then collected in the liquid preparation tank 18. At this time, a necessary amount of the mixed solvent and the surfactant are replenished from the replenishing tank TN2, and a necessary amount of water is replenished from the replenishing tank TN5. Maintained. And the cleaning agent of the liquid adjustment tank 18 is replenished to the ultrasonic cleaning tank 1 as needed.

  Here, it is as follows when a series of operation | movement of the distillation system SYS is confirmed. First, in a state where the connection with the reserve tank 4 is closed, the entire system is evacuated to about 0.1 atm, and then the connection with the reserve tank 4 is opened. From the reserve tank 4 to the reboiler 10, the cleaning liquid after use (deterioration) Liquid).

  Next, the heating operation of the reboiler 10 is started, and the total reflux operation is started while the reflux tank 12 and the intermediate tank 13 are in a predetermined hold-up state. Thereafter, when the predetermined operation time is completed, the heating operation of the reboiler 10 is stopped.

  Next, the connection with the reserve tank 4 is closed, and the reflux tank 12 and the intermediate tank 13 are cooled to the room temperature level. Thereafter, the entire system is opened to the atmosphere, and the regenerated liquid collected in the reflux tank 12 and the intermediate tank 13 is moved to the preparation tank 18 together with the replenisher from the replenisher tanks TN2 and TN5. Further, the concentrated liquid of the reboiler 10 is moved to the drain 19 to finish the batch processing.

  Although not particularly limited, this distillation system SYS is designed to regenerate 200 liters of deteriorated liquid in a batch operation of about 2 hours.

  By the way, in the distillation system SYS of FIG. 2, although the liquid adjustment tank 18 connected to the ultrasonic cleaning tank 1 was provided, it is not specifically limited. FIG. 3 is a modification of FIG. 2 and shows a distillation system that supplies the regenerated liquid collected in the reflux tank 12 and the intermediate tank 13 to the reserve tank 4 together with the replenishing liquid from the replenishing tanks TN2 and TN5. .

  In FIGS. 2 and 3, the distillation system SYS is disposed in the ultrasonic cleaning tank, but it goes without saying that the object to be disposed is not particularly limited, including other immersion cleaning tanks.

SYS distillation system 10 reboiler 11 distillation tower 12 reflux tank 13 intermediate tank

Claims (12)

To a base solvent of 50 to 99 Vol% in which a glycol ether solvent is added to a naphthene hydrocarbon solvent containing naphthene as a main component,
A detergent composition containing 100 to 50 Vol% of a surfactant and water as a whole, substantially containing 100 Vol%,
A detergent composition, wherein the surfactant has an HLB of 10 to 14.   The cleaning composition according to claim 1, wherein boiling points of the naphthene hydrocarbon solvent and the glycol ether solvent are 200 to 220 ° C under normal pressure.   The cleaning composition according to claim 1 or 2, wherein a content Vol ratio of the naphthene hydrocarbon solvent and the glycol ether solvent is 6: 1 to 1: 1.   The detergent composition according to any one of claims 1 to 3, wherein the surfactant is an ethylene oxide single addition type or an ethylene oxide and propylene oxide addition type nonionic surfactant. The surfactant is a monomeric type of one hydrophobic chain and one hydrophilic group type,
The detergent composition according to any one of claims 1 to 4, wherein the surfactant content is 50 to 90 Vol% with respect to the total amount of the surfactant and water. The surfactant is a gemini type formed by binding a surfactant of one hydrophobic chain and one hydrophilic group with a spacer,
The detergent composition according to any one of claims 1 to 4, wherein the surfactant content is 10 to 50 Vol% with respect to the total amount Vol of the surfactant and water.   The cleaning agent after use is processed in a predetermined distillation system to concentrate and regenerate the base solvent, and the required amount of surfactant and water are added to the base solvent to be reused as a cleaning agent. Item 7. A cleaning composition according to any one of Items 1 to 6. The distillation system comprises:
A reboiler that receives the cleaning agent after use, a distillation column that receives steam from the reboiler, a distilling water from the distillation column, a reflux tank that is configured to be able to recirculate to the distillation column, The detergent composition according to claim 7, comprising an intermediate tank configured to receive canned water and to be returned to the reboiler. While the cleaning agent after use is continuously used while removing the foreign matter and circulating between the immersion cleaning tank and the reserve tank,
The cleaning composition according to claim 7 or 8, wherein a part of the cleaning agent for the reserve tank is periodically supplied to the distillation system to be regenerated.   The throughput of the distillation system is 50 to 300 liters per time, and after the distillation process for 0.5 to 3 hours, each concentrated regeneration solution in the reflux tank and the intermediate tank is supplemented with the necessary constituent composition. The cleaning composition according to any one of claims 7 to 9, wherein the cleaning composition is configured to be supplied to a reserve tank.   The throughput of the distillation system is 50 to 300 liters per time. After the distillation process for 0.5 to 3 hours, the concentrated regenerated liquids in the reflux tank and the intermediate tank are supplemented with the necessary constituent compositions. And the cleaning composition in any one of Claims 7-9 comprised so that it may be stored by the adjustment tank connected to the immersion cleaning tank.   The cleaning agent according to any one of claims 1 to 6, wherein the reboiler receives a cleaning agent after use, the distillation column receives steam from the reboiler, and the distillate from the distillation column is distilled. A distillation system comprising: a reflux tank configured to be refluxed to a tower; and an intermediate tank configured to receive the bottoms from the distillation tower and be refluxed to a reboiler.