JP2019005681A - Washing device - Google Patents

Abstract

To provide a cleaning device capable of removing oil from a washing object continuously and stably for a long period even when water is reused as the washing liquid.SOLUTION: A cleaning device comprises a cleaning liquid preparation part that mixes water with a gas to prepare a washing liquid containing fine bubbles, a washing tank connected with the washing liquid preparation part to bring a washing object in contact with the washing liquid, and to generate oil-containing water, a mixture of oil with the washing liquid, by removing the oil sticking to the washing object, an oil content aggregation part connected with the washing tank to coarsen oil content in the oil-containing water by aggregation, an oil water separation part connected to the oil content aggregation part to separation part that separates oil content from water content of the oil-containing water containing coarsened oil content by an oil water separation filter the base material of which forms a hydrophilic and oil-repellent oil water separator, and pipes which connect the oil water separation part with the water liquid preparation part to transfer the water content separated in the oil water separation part to the water liquid preparation part, where the oil water separator contains a fluorine-based compound having oil-repellency provided groups and hydrophilicity provided groups.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a cleaning apparatus for a cleaning object to which oil is attached.

  2. Description of the Related Art A cleaning apparatus that uses, as a cleaning liquid, bubble-containing water containing fine bubbles called microbubbles or nanobubbles is known. Since the cleaning liquid containing fine bubbles has a high oil removing capability, oil stains can be efficiently removed without using a detergent. For this reason, a cleaning apparatus using a cleaning liquid containing fine bubbles is used as an apparatus for cleaning various parts produced in a parts factory, for example.

  As a cleaning apparatus that uses a cleaning liquid containing fine bubbles, Patent Document 1 discloses a cleaning apparatus that injects a cleaning liquid containing fine bubbles onto an object to be cleaned contained in a mesh bag. In this Patent Document 1, the sprayed cleaning liquid is temporarily stored in a bathtub, washed away from the object to be cleaned, and the oil floating on the bathtub is recovered by an oil skimmer. A cleaning apparatus configured to be reused is disclosed.

  Patent Document 2 discloses a cleaning device that ejects a cleaning liquid containing fine bubbles to an object to be cleaned immersed in a cleaning liquid in a cleaning container. In this patent document 2, the cleaning liquid is purified by using an air spray unit for collecting the liquid oil film floating on the surface of the cleaning liquid, an overflow tank for recovering the liquid oil film and performing oil-water separation, and an oil recovery device. Thus, a cleaning apparatus configured to be used for a long period of time is disclosed. This Patent Document 2 describes a suction device such as an aspirator or a scraping device using a bowl-like material as an oil recovery device.

JP2015-112506A JP 2007-301529 A

  It is preferable that the cleaning apparatus can stably remove the oil to be cleaned with a small amount of cleaning liquid over a long period of time and with high efficiency. As described in Patent Documents 1 and 2, reusing the cleaning liquid (oil-containing water) after cleaning is an effective method for reducing the amount of water used. However, according to the study of the present inventor, when water from which oil has been removed using an oil skimmer or aspirator is reused, the oil is accumulated in the water, and the washing efficiency may decrease with the passage of time from the start of washing. It has been found.

  The present invention has been made in view of the above circumstances, and is a cleaning device that can continuously and stably remove oil from an object to be cleaned even when water is reused as a cleaning liquid. The purpose is to provide.

In order to solve the above problems, the cleaning apparatus of the present invention has the following configuration.
[1] A cleaning apparatus for an object to be cleaned to which oil is attached, the cleaning liquid preparing unit for preparing a cleaning liquid containing fine bubbles by mixing water and gas, and the cleaning liquid preparing unit connected to the cleaning target A cleaning tank for contacting the cleaning object with the cleaning liquid to remove the oil adhering to the cleaning target, and generating oil-containing water that is a mixture of the oil and the cleaning liquid; and The oil-containing agglomerated part that aggregates and coarsens the oil content in the oil-containing water and the oil-containing water that is connected to the oil agglomerated part and contains the coarsened oil content has hydrophilic oil repellency on the base material An oil / water separation unit that separates oil and water by an oil / water separation filter that forms an oil / water separator, and the oil / water separation unit and the cleaning liquid preparation unit are connected, and the water separated by the oil / water separation unit is removed from the cleaning liquid. A pipe for transfer to the preparation unit, and Water separator is characterized in that it comprises a fluorine-based compound having a oil repellency imparting group and hydrophilicity-imparting group.

  In the cleaning device having such a configuration, after the oil content in the oil-containing water is aggregated in the oil content aggregation unit, the oil content and the water content in the oil-containing water are separated in the oil-water separation unit. Separation can be performed efficiently. The oil / water separation filter used in the oil / water separation unit includes an oil / water separator containing a fluorine-based compound having an oil repellency-imparting group and a hydrophilicity-imparting group, and has high hydrophilic oil repellency. Hard to mix. For this reason, even if it uses the isolate | separated water | moisture content as a raw material of a washing | cleaning liquid, the oil of a washing | cleaning target object can be removed stably stably over a long period of time.

[2] The fluorine-based compound includes one or more of compounds having a structure represented by the following formulas (1) to (4).

In the above formulas (1) and (2), Rf ¹ and Rf ² are the same or different, each having 1 to 6 carbon atoms and a linear or branched perfluoroalkyl group, and Rf ³ is carbon A number 1-6, which is a linear or branched perfluoroalkylene group;
In the above formulas (3) and (4), Rf ⁴ , Rf ⁵ and Rf ⁶ are the same or different, each having 1 to 6 carbon atoms and a linear or branched perfluoroalkylene group, and Z is Any one of an oxygen atom, a nitrogen atom, a CF ₂ group and a CF group;
In the above formulas (2) and (4), R is a linking group that is a divalent organic group;
Moreover, in said formula (1)-(4), X is any one hydrophilicity imparting group selected from the group which consists of an anionic type, a cationic type, and an amphoteric type.

[3] The oil-water separator is bonded to the base material by at least one of an organic binder and an inorganic binder, or both.

[4] The substrate is made of at least a porous body that is permeable to moisture.

[5] The oil aggregation part is a coalescer.

[6] The oil aggregation unit is an oil floating device.

[7] The apparatus further includes a pipe connected to the oil / water separator and the oil agglomeration part to transfer the water separated by the oil / water separator to the oil agglomeration part.

[8] Further, it is characterized in that a pipe is provided for returning the water separated in the oil / water separator to the oil / water separator.

  ADVANTAGE OF THE INVENTION According to this invention, even if it reuses water as a washing | cleaning liquid, the washing | cleaning apparatus which can remove the oil of a washing | cleaning target object stably over a long period of time can be provided.

It is a block diagram which shows the structure of the washing | cleaning apparatus in 1st embodiment. It is sectional drawing of an example of the oil content aggregation apparatus which can be used as an oil content aggregation part of the washing | cleaning apparatus in 1st embodiment. It is sectional drawing of another example of the oil content aggregation apparatus which can be used as an oil content aggregation part of the washing | cleaning apparatus in 1st embodiment. It is sectional drawing of an example of the oil-water separator which can be used as an oil-water separator of the washing | cleaning apparatus in 1st embodiment. It is sectional drawing of another example of the oil-water separator which can be used as an oil-water separator of the washing | cleaning apparatus in 1st embodiment. It is a block diagram which shows the structure of the washing | cleaning apparatus in 2nd embodiment. It is a block diagram which shows the structure of the washing | cleaning apparatus in 3rd embodiment.

  Hereinafter, a cleaning apparatus according to an embodiment to which the present invention is applied will be described with reference to the drawings. The embodiments described below are specifically described for better understanding of the gist of the present invention, and do not limit the present invention unless otherwise specified. In addition, in the drawings used in the following description, in order to make the features of the present invention easier to understand, there is a case where a main part is shown in an enlarged manner for convenience, and the dimensional ratio of each component is the same as the actual one. Not necessarily.

<First embodiment>
FIG. 1 is a configuration diagram showing the configuration of the cleaning device in the first embodiment.
The cleaning apparatus 10 of the present embodiment includes a cleaning liquid preparation unit 11, a cleaning tank 12, an oil agglomeration unit 16, an oil / water separation unit 17, a pipe 18 that connects the oil / water separation unit 17 and the cleaning liquid preparation unit 11, and a cleaning liquid. A pipe 24 is provided to connect the preparation unit 11 and the injector 14 of the cleaning tank 12.

The cleaning liquid preparation unit 11 prepares a cleaning liquid by mixing water and gas. The cleaning liquid is bubble-containing water containing fine bubbles called microbubbles or nanobubbles.
The pipe 24 uses the pump 25 to transfer the cleaning liquid prepared by the cleaning liquid preparation unit 11 to the injector 14 of the cleaning tank 12.

  The cleaning tank 12 has a mesh container 13 for storing the cleaning object 1 therein, an injector 14 for injecting the cleaning liquid 2 prepared by the cleaning liquid preparation unit 11, and the cleaning object 1 and the cleaning liquid 2 in contact with each other. It is a mixture of oil and cleaning liquid produced by removing the oil adhering to the cleaning object 1, and has a drain port 15 for oil-containing water 5 containing oil 3 and moisture 4. The oil-containing water drain 15 is located at a position lower than the mesh container 13 so that the oil-containing water 5 does not come into contact with the object 1 to be cleaned.

  The oil content aggregation unit 16 includes an oil content aggregation device that aggregates the oil content in the oil-containing water 5. As the oil aggregating apparatus, a coalescer and an oil floating apparatus can be used. An example of the oil content aggregating apparatus will be described later.

  The oil / water separator 17 has an oil / water separator that separates oil and water by an oil / water separator filter. The oil-water separation filter includes a base material and an oil-water separator having hydrophilic oil repellency formed on the base material. Examples of the oil / water separator and the oil / water separator filter will be described later.

The pipe 18 transfers the water separated by the oil / water separator 17 to the cleaning liquid preparation unit 11.
The pipe 18 is connected to the oil return pipe 20 connected to the oil / water separator 17 and the oil aggregating part 16 via the valve 19. The oil return pipe 20 is provided with a pump 21, and when oil is mixed in a large amount of water separated by the oil / water separator 17, the oil content agglomeration part 16 converts oil containing oil through the oil return pipe 20. Can be returned to. Further, the pipe 18 is connected via a valve 22 to an extraction pipe 23 for taking out the water separated by the oil / water separator 17. When oil is excessively mixed in the water separated by the oil / water separation unit 17 and separation of the oil and water becomes difficult, the water is taken out by the take-out pipe 23 and new water is washed. It can be supplied to the preparation unit 11.

  In the cleaning apparatus 10 of the present embodiment, the cleaning liquid 2 prepared in the cleaning liquid preparation unit 11 is sent to the injector 14 of the cleaning tank 12 through the pipe 24. In the cleaning tank 12, the cleaning object 1 accommodated in the mesh container 13 and the cleaning liquid 2 sprayed from the injector 14 come into contact with each other, so that the oil adhering to the cleaning object 1 is removed, and the oil 3 and moisture are removed. 4 and oil-containing water 5 is produced.

  The oil-containing water 5 is sent to the oil aggregation unit 16 through the drain port 15. In the oil aggregation unit 16, the oil in the oil-containing water 5 aggregates to produce coarse oil particles. The oil-containing water 5 containing coarse oil particles is sent to the oil / water separator 17 where it is separated into oil and water. The separated oil is taken out to the outside. The separated moisture is sent to the cleaning liquid preparation unit 11 through the pipe 18. The water sent to the cleaning liquid preparation unit 11 is used as a raw material for the cleaning liquid.

[Oil content coagulator]
FIG. 2 is a cross-sectional view of an example of an oil content aggregating apparatus that can be used as the oil content aggregating unit of the cleaning device in the first embodiment.
In FIG. 2, the oil content aggregating apparatus 30 is a coalescer having a hollow cylindrical casing 31 and a coarse filter 33 disposed inside the casing 31 and accommodated in a filter case 32. The casing 31 has an inflow port 31a at the center of the lower surface, a drain port 31b at the bottom of the side surface, and an oil drain port 31c at the upper side of the side surface. The inflow port 31 a is connected to the drain 15 of the cleaning tank 12 and the return pipe 20.

  The filter case 32 is a cylindrical case that accommodates the coarse filter 33 therein, and a large number of through holes 32a are formed on the peripheral surface. Such a filter case 32 prevents deformation and outflow of the coarse filter 33, and for example, a net-like cylinder can be used.

  The coarse filter 33 preferably includes a porous body having lipophilicity (hydrophobicity). The porous body is preferably a lipophilic fiber sheet. The oleophilic fiber sheet may be any of woven fabric, knitted fabric, and non-woven fabric. As the material of the fiber sheet, hydrophobic fibers such as polypropylene fibers and polyethylene fibers can be used. Moreover, you may use the lipophilic fiber sheet which provided the lipophilic property by giving lipophilic processing to a fiber sheet. As a method for imparting lipophilicity to the fiber sheet, a normal method, for example, a method of treating the fiber sheet or the fiber (raw yarn) serving as the material with a water repellent agent can be used. As the water repellent, for example, a silicone-based water repellent such as dimethyl silicone, a paraffin-based water repellent, or a wax-based water repellent can be used. As a method of treating with a water repellent, a method such as putting, dipping, spraying or exhausting can be used. Further, after treatment with a water repellent agent, heat treatment may be performed as necessary.

  The coarse filter 33 adsorbs and aggregates the fine oil component 3 in the oil-containing water 5, thereby generating a coarse oil component 3a. Specifically, the coarsening means that an oil having a diameter (droplet diameter) of, for example, about 0.1 to 50 μm is changed to an oil having a diameter of, for example, 0.1 mm or more.

  When the oil-containing water 5 is pumped to the inlet 31 a of the housing 31 in the oil aggregation device 30, the oil-containing water 5 rises in the housing 31 and contacts the coarse filter 33. The oil in the oil-containing water 5 that has come into contact with the coarse filter 33 is adsorbed by the coarse filter 33, aggregates and coarsens, and then desorbs from the coarse filter 33. The coarse oil component 3a desorbed from the coarse filter 33 is likely to float in the oil-containing water 5 due to the difference in specific gravity with the water 4, so that a part of the oil component 3a accumulates on the upper portion of the housing 31 and the oil film 3b is formed. Form. The oil film 3b is taken out from the oil discharge port 31c. The remaining coarse oil 3a remains in the oil-containing water 5 and is taken out from the drain 31b.

FIG. 3 is a cross-sectional view of another example of an oil content aggregating apparatus that can be used as the oil content aggregating part of the cleaning device in the first embodiment.
In FIG. 3, the processing tank 41 of the oil content aggregating apparatus 40 is divided into three tanks of a first tank 41a, a second tank 41b, and a third tank 41c by two partition plates 42a and 42b opened at the lower side. Thus, the oil levitation device floats the oil in the second tank 41b. An inlet 43a is provided on the side surface of the first tank 41a, and a drain outlet 43b is provided on the side surface of the third tank 41c. A dam plate 44 is provided at the bottom of the second tank 41b.

  In the oil aggregating apparatus 40, the oil-containing water 5 transferred to the inlet 43a of the first tank 41a flows into the second tank 41b through the opening below the partition plate 42a. The oil-containing water 5 that has flowed into the second tank 41b rises along the barrier plate 44, then descends, and flows into the third tank 41c through the opening below the partition plate 42b. In the second tank 41b, when the oil-containing water 5 rises and falls, the oil component 3 rises due to the difference in specific gravity between the oil component 3 and the moisture 4, and the oil components come into contact with each other and aggregate. The coagulated and coarsened oil component 3a easily floats in the oil-containing water 5 due to the difference in specific gravity with the moisture 4, so that a part of the oil component 3a accumulates on the upper part of the second tank 41b to form the oil film 3b. The oil film 3b is directly taken out to the outside. The remaining coarse oil component 3a remains in the oil-containing water 5 and is taken out from the drain outlet 43b.

[Oil-water separator]
FIG. 4 is a cross-sectional view of an example of the oil / water separator that can be used as the oil / water separator of the cleaning device according to the first embodiment.
The oil / water separation device 50 includes a liquid tank 51 and an oil / water separation filter 52 formed in a bottomed cylindrical shape provided in the liquid tank 51. The upper part of the liquid tank 51 is an open surface 51a and serves as an inlet for oil-containing water. A water outlet 51b is integrally formed on the lower side surface of the liquid tank 51, and an oil drain passage 51c is integrally formed on the upper side surface. The oil drainage channel 51 c guides the oil component separated by the oil / water separation filter 52 to the outside of the liquid tank 51. The oil drainage channel 51c can be formed, for example, by notching a part of the upper edge portion of the liquid tank 51 and expanding outward.

  An oil drain port 52c is formed in the vicinity of the open end 52e of the oil / water separation filter 52, that is, in a portion in contact with the oil drain passage 51c, so that the separated oil component flows toward the oil drain passage 51c. Such an oil discharge port 52c includes, for example, an opening formed on the peripheral surface of the oil / water separation filter 52 and a cylindrical member connected to the opening. The cylindrical member can be joined to the peripheral surface of the oil / water separation filter 52 by sewing or heat fusion.

  On the inner surface 52a side of the oil / water separation filter 52, a dispersion plate 53 such as a mesh member is further provided. The dispersion plate 53 has a bottomed cylindrical shape, for example, and bends the upper edge portion outward to be separated above the oil / water separation filter 52 and hooked on the edge portion on the open surface 51a side of the liquid tank 51. Locked. When such a dispersion plate 53 puts oil-containing water into the liquid tank 51, the dispersion plate 53 temporarily receives the oil-containing water, so that the oil-containing water greatly decreases in speed when passing through the dispersion plate 53. Thus, the impact of oil-containing water applied to the oil / water separation filter 52 can be greatly reduced. In addition, air entrainment can be suppressed, and even if a relatively large size solid such as dust is mixed in the oil-containing water, it can be removed in advance, and the oil-water separation filter 52 is blocked by dust. To prevent.

  On the outer surface 52b side of the oil / water separation filter 52, a support member 54 is disposed in an overlapping manner. The support member 54 has, for example, a bottomed cylindrical shape, and is bent and hooked on the edge of the liquid tank 51 on the open surface 51a side by being bent outward so that the upper edge is bent outward. The The support member 54 is composed of a hard member through which at least moisture can pass, for example, a metal material (punching plate) in which a large number of openings are formed. Such a support member 54 supports the flexible oil / water separation filter 52 from the outer surface 52b side.

  By forming such a support member 54 so as to overlap the outer surface 52b side of the oil / water separation filter 52, for example, even if a large amount of oil-containing water flows into the oil / water separation filter 52 all at once, The separation filter 52 can be prevented from being deformed and the bottom can be prevented from being damaged, and the oil-water separation and filtration can be performed efficiently. The support member 54 may be made of a ceramic material having a relatively large hole or a hard plastic material having an opening.

  An oil tank 55 is disposed at the outflow end 51e of the oil discharge passage 51c to receive the oil flowing out through the oil discharge passage 51c. Furthermore, the oil / water separator 50 includes a liquid tank moving means 56 that moves the liquid tank 51 up and down. It is preferable to further include a lid member that covers the open surface 51 a of the liquid tank 51 and a cover member that covers the open surface 55 a of the oil tank 55.

FIG. 5 is a cross-sectional view of another example of the oil / water separator that can be used as the oil / water separator of the cleaning device in the first embodiment.
The oil / water separator 60 includes a cylindrical container 61 formed in a bottomed cylindrical shape, a support 63 extending upward from the center of the bottom of the cylindrical container 61, and an oil / water separation fixed to the support 63 via sealants 64a and 64b. And a filter 65. The cylindrical container 61 has an oil-containing water inlet 62a at the center side surface, a moisture outlet 62b at the center of the bottom surface, and an oil separation outlet 62c at the upper side surface. The oil / water separation filter 65 is a cylindrical body whose upper portion is closed, and the inner space of the oil / water separation filter 65 is connected to the moisture outlet 62b.

  In the oil / water separator 60, the oil-containing water 5 is stored in the cylindrical container 61 through the inflow port 62a. The moisture 4 in the oil-containing water 5 stored in the cylindrical container 61 passes through the oil / water separation filter 65 and permeates into the inner space of the oil / water separation filter 65. The moisture 4 that has penetrated into the inner space of the oil / water separation filter 65 is taken out from the moisture outlet 62b. On the other hand, the oil content in the oil-containing water floats in the oil-containing water 5 without passing through the oil-water separation filter 65, and the oil content that has floated accumulates in the upper part of the cylindrical container 61 to form the oil film 3b. The oil film 3b is taken out from the oil separation outlet 62c.

[Oil-water separation filter]
The oil-water separation filter includes a base material and an oil-water separator having hydrophilic oil repellency formed on the base material.

(Base material)
The substrate is preferably made of a porous body that can at least transmit moisture. As the substrate, a fiber assembly can be used. As the fiber assembly, fabrics such as knitted fabrics, woven fabrics, and nonwoven fabrics, twisted yarns, long hair fibers, and the like can be used. The material of the fiber assembly is not particularly limited as long as it is a fibrous material or a porous material capable of forming a water flow path to be separated, and may be an organic material or an inorganic material. Also good. Furthermore, it may be a composite of an organic substance and an inorganic substance. Accordingly, examples of the base material in the oil-water separation filter of the present embodiment include organic fibrous materials or porous materials, and inorganic fibrous materials or porous materials.

  Here, the organic material that can be used as the base material is not particularly limited. Specifically, for example, cellulose filter paper, filter cloth (polyester, polyethylene, polypropylene, polytetrafluoroethylene, nylon, Polyimide, polyacrylonitrile, polysulfone, polyethersulfone, polyphenylene sulfide, etc.), non-woven filter (polyester, polyethylene, polypropylene, rayon, nylon, polyphenylene sulfide, etc.), fiber filter (resin, glass, ceramics, metal), sintered filter ( And powders or fibers of metals, ceramics, plastics and the like directly bonded by heat and pressure).

  In the fiber assembly used as the base material, the diameter of the pores serving as moisture channels is preferably 0.1 to 150 μm, more preferably 0.5 to 75 μm, and 1 to 50 μm. Further preferred. When the pore diameter exceeds 150 μm, it is not preferable because oil (oil) starts to pass. On the other hand, when the pore diameter is within the above range, oil permeation does not occur and a water flow rate in a practically suitable range is preferable.

(Oil-water separator)
The oil / water separator includes a fluorine-based compound having an oil repellency-imparting group and a hydrophilicity-imparting group. The oil / water separator imparts hydrophilic oil repellency to the oil / water separation filter by the presence of the oil repellency imparting group and the hydrophilicity imparting group. When oil-containing water comes into contact with the oil-water separation filter, the oil is repelled by the oil-water separation filter to form oil droplets having a large contact angle and aggregate to float up the oil-containing water. On the other hand, moisture maintains wettability with a small contact angle and passes through the oil-water separation filter. As a result, oil and moisture are separated. By such an action, the oil / water separation filter can not only selectively separate the water content of the oil-containing water but also increase the water transmission rate. In addition, it is preferable that the oil-water separator is layered on the base material (fiber assembly), and it is further preferable that the oil-water separator is impregnated to the inside in the thickness direction of the base material.
As a fluorine-type compound contained in an oil-water separator, the compound shown by following formula (1)-(4) can be mentioned, for example. A fluorine-type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

In the above formulas (1) and (2), Rf ¹ and Rf ² are the same or different from each other, each having 1 to 6 carbon atoms and a linear or branched perfluoroalkyl group. Rf ³ is a linear or branched perfluoroalkylene group having 1 to 6 carbon atoms. Rf ¹ and Rf ² are each preferably the same or different from each other and each having 1 to 4 carbon atoms and is a linear or branched perfluoroalkyl group. Rf ³ has 1 to 4 carbon atoms, and is preferably a linear or branched perfluoroalkylene group.

In the above formulas (3) and (4), Rf ⁴ , Rf ^5, and Rf ⁶ are the same or different from each other, each having 1 to 6 carbon atoms and a linear or branched perfluoroalkylene group. Z includes an oxygen atom, a nitrogen atom, a CF ₂ group, or a CF group. When Z contains a nitrogen atom or a CF group, a perfluoroalkyl group branched from Z may be bonded to Z. Rf ⁴ , Rf ⁵ and Rf ⁶ are each preferably the same or different from each other and each having 1 to 4 carbon atoms and a linear or branched perfluoroalkylene group.

  Moreover, in said formula (2) and (4), R is a coupling group which is a bivalent organic group. Here, R may be a linear or branched organic group.

  Moreover, in said formula (1)-(4), X is any one hydrophilicity imparting group selected from the group which consists of an anionic type, a cationic type, and an amphoteric type.

  The fluorine-based compounds represented by the above formulas (1) to (4) have a perfluoroalkyl group and a perfluoroalkylene group as the oil repellency-imparting group, and are composed of an anionic type, a cationic type, and an amphoteric type as the hydrophilicity-providing group. Since it has any one hydrophilic imparting group selected from the group, it acts as a hydrophilic oil repellent having high hydrophilic oil repellency.

[Linear or branched fluorine compound]
In the linear or branched fluorine-based compound represented by the above formula (1) or the above formula (2), a nitrogen-containing perfluoroalkyl group composed of Rf ¹ and Rf ² and a nitrogen-containing perfluoroalkylene group composed of Rf ³ are It constitutes an oil repellency-imparting group.
Further, in the above formula (1) or the formula (2) in the fluorine-based compound shown, the oil repellency is imparted group Rf ¹ ～Rf ³ in the range sum of 4 to 18 pieces of carbon atoms of the fluorine is bonded It is preferable that If the number of carbons to which fluorine is bonded is less than 4, it is not preferable because the oil repellent effect is insufficient.

Here, in the above formula (2), R is a linking group that connects the oil repellency-imparting group and the hydrophilicity-imparting group in the molecular chain. The structure of the linking group R is not particularly limited as long as it is a divalent organic group. Specific examples of the linking group R include, for example, an oxygen atom [—O—], a carbonyl group [—C (═O) —], an imino group [—NH—], and a sulfonyl group [—S (═O). _2— ], —OP (═O) (O ⁻ ) O— group, hydrocarbon group having 1 to 20 carbon atoms, and combinations thereof. Further, the linking group R may contain one or more selected from a polyoxyalkylene group and an epoxy group. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The hydrocarbon group may be a chain hydrocarbon group or a cyclic hydrocarbon group. The chain hydrocarbon group may be linear or branched. Examples of the hydrocarbon group include an alkylene group, an alkenylene group, and an arylene group. The imino group and the hydrocarbon group may have a substituent.

  The linking group R may or may not contain one or more bonds selected from an ether bond, an ester bond, an amide bond and a urethane bond in the molecular chain. The amide bond includes a carboxylic acid amide bond and a sulfonamide bond. The ester bond includes a carboxylic acid ester bond, a sulfonic acid ester bond, and a phosphate ester bond.

  The linking group R is preferably selected and introduced as appropriate according to the properties desired to be imparted to the fluorine-based compound. Specifically, for example, when it is desired to adjust the solubility in a solvent such as water or an organic solvent, or when it is desired to improve the durability by improving the adhesion to the base material (porous body). The method includes adjusting the chain length of a linear or branched hydrocarbon group that adjusts the presence or type of polar groups that affect the intermolecular interaction, and the chemical structure included in the substrate. Introducing a structure similar to the part.

Moreover, in said formula (1) or said formula (2), X is any one hydrophilicity imparting group selected from the group which consists of an anionic type, a cationic type, and an amphoteric type.
Hereinafter, the structure of the fluorine-based compound will be described by dividing the hydrophilic imparting group X into cases.

(Anion type)
When the hydrophilic imparting group X is an anionic type, the above-mentioned X is “—CO ₂ M ¹ ”, “—SO ₃ M ¹ ”, “—OSO ₂ M ¹ ”, “—OP (OH) O _{2 at the terminal.} “M ¹ ”, “—OPO ₃ M ¹ ₂ ”, “═O ₂ PO ₂ M ¹ ” or “—PO (OH) _y (OM ¹ ) _{2 -y} ” (M ¹ is an alkali metal or alkaline earth metal) , Mg, Al, R ¹ R ² R ³ R ⁴ N ⁺ ; R ^{1 to} R ⁴ are each a hydrogen atom or an independent straight chain or branched chain having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Alkyl group). When M ¹ is a divalent metal (alkaline earth metal, Mg), two identical anions may be bonded to M ¹ or two different anions are bonded. Also good. When M ¹ is aluminum, three identical anions may be bonded to M ¹ or two or three different anions may be bonded.

  Examples of the alkali metal include lithium (Li), sodium (Na), potassium (K), and cesium (Cs). Examples of the alkaline earth metal include calcium (Ca), strontium (Sr), and barium (Ba).

As the quaternary ammonium salt ^{(R 1 R 2 R 3 R} 4 N +), up R 1 to R ⁴ is from 1 to 20 carbon atoms which independently hydrogen atom or each, preferably up to 10 carbon atoms There is no particular limitation as long as it is a linear or branched alkyl group. Here, it is preferable that the alkyl group has 20 or less carbon atoms because the hydrophilic oil repellency is not impaired. More specifically, examples of the compound in which R ¹ R ² R ³ R ⁴ are all the same include (CH ₃ ) ₄ N ⁺ , (C ₂ H ₅ ) ₄ N ⁺ , and (C ₃ H ₇ ) ₄ N ^+. , (C ₄ H ₉ ) ₄ N ⁺ , (C ₅ H ₁₁ ) ₄ N ⁺ , (C ₆ H ₁₃ ) ₄ N ⁺ , (C ₇ H ₁₅ ) ₄ N ⁺ , (C ₈ H ₁₇ ) ₄ N ⁺ , (C ₉ H ₁₉ ) ₄ N ⁺ , (C ₁₀ H ₂₁ ) ₄ N ^{+ and the} like. In addition, when R ¹ R ² R ³ is all a methyl group, for example, R ⁴ is (C ₂ H ₅ ), (C ₆ H ₁₃ ), (C ₈ H ₁₇ ), (C ₉ H ₁₉ ), Examples of the compound include (C ₁₀ H ₂₁ ), (C ₁₂ H ₂₅ ), (C ₁₄ H ₂₉ ), (C ₁₆ H ₃₃ ), and (C ₁₈ H ₃₇ ). Further, when all of R ¹ R ² are methyl groups, for example, all of R ³ R ⁴ are (C ₈ H ₁₇ ), (C ₁₀ H ₂₁ ), (C ₁₂ H ₂₅ ), (C ₁₄ H ₂₉ ). , (C ₁₆ H ₃₃ ), (C ₁₈ H ₃₇ ) and the like. Furthermore, examples of the case where R ¹ is a methyl group include compounds in which R ² R ³ R ⁴ are all (C ₄ H ₉ ), (C ₈ H ₁₇ ), and the like.

By the way, in an application that is used in contact with water, such as an oil / water separation filter, the oil / water separator is desired to have durability against water and durability of a hydrophilic oil-repellent effect. From the above viewpoint, the fluorine-based compound used in the present embodiment is desirably a hardly soluble compound having low solubility in water. That is, when the hydrophilic imparting group X is an anion type, the counter ion M ¹ is preferably an alkaline earth metal, Mg, Al, and Ca, Ba, Mg are particularly excellent in hydrophilic oil repellency, It is preferable because of its low solubility in water.

(Cation type)
When the hydrophilic imparting group X is a cation type, the above X has “—N ⁺ R ⁵ R ⁶ R ⁷ • Cl ⁻ ”, “—N ⁺ R ⁵ R ⁶ R ⁷ • Br ⁻ ”, “— ^{N + R 5 R 6 R 7} · I - "" ^{- N + R 5 R 6 R} 7 · CH 3 SO 3 - , "" ^{- N + R 5 R 6 R} 7 · R 7 SO 4 - "," ^{-N + R 5 R 6 R 7} · NO 3 - "," ^{(- N + R 5 R 6} R 7) 2 CO 3 2- "or" ^{(-N + R 5 R 6 R} 7) 2 SO 4 2 ⁻ ”(R ^{5 to} R ⁷ are each a hydrogen atom or an independent linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms). Here, it is preferable that the number of carbon atoms is 20 or less because the hydrophilic oil repellency is not impaired.

(Bisexual)
In the case where the hydrophilic imparting group X is an amphoteric type, the above-mentioned X is at the end of the carboxybetaine type “—N ⁺ R ⁸ R ⁹ (CH ₂ ) _n CO ₂ ⁻ ”, and the sulfobetaine type “—N ⁺ R”. ⁸ R ⁹ (CH ₂ ) _n SO ₃ ⁻ ”, amine oxide type“ —N ⁺ R ⁸ R ⁹ O ⁻ ”, or phosphobetaine type“ —OPO ₃ ^— (CH ₂ ) _n N ⁺ R ⁸ R ⁹ R ”. ¹⁰ "or" _{^{-N + R 8 R 9 (CH}} 2) n OPO 3 - R 11 "(n is an integer of from 1 to ^{5, R 8, R 9, R} 10 is a hydrogen atom or independent 1 carbon atoms 12 linear or branched alkyl groups, and R ¹¹ is a linear or branched alkyl group having 1 to 12 carbon atoms. Here, it is preferable that the number of carbon atoms is 12 or less because the hydrophilic oil repellency is not impaired.

[Cyclic fluorinated compound]
In the cyclic fluorine-based compound represented by the above formula (3) or the above formula (4), the nitrogen-containing perfluoroalkylene group composed of Rf ⁴ , Rf ⁵ and Rf ⁶ and further Z constitute an oil repellency-imparting group.
Further, in the above formula (3) or the formula (4) in the fluorine compound annular shown, of the repellent Rf ⁴ ~Rf ⁶ and wherein Z is an oily imparting group, the total carbon number of fluorine is bonded is 4 A range of 18 is preferable, and a range of 5 to 12 is preferable. If the number of carbons to which fluorine is bonded is less than 4, it is not preferable because the oil repellent effect is insufficient.

Here, in the above formula (4), R is a linking group that connects the oil repellency-imparting group and the hydrophilicity-imparting group in the molecular chain. The structure of the linking group R is not particularly limited as long as it is a divalent organic group. Specific examples of the linking group R include, for example, an oxygen atom [—O—], a carbonyl group [—C (═O) —], an imino group [—NH—], and a sulfonyl group [—S (═O). _2— ], —OP (═O) (O ⁻ ) O— group, hydrocarbon group having 1 to 20 carbon atoms, and combinations thereof. Further, the linking group R may contain one or more selected from a polyoxyalkylene group and an epoxy group. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The hydrocarbon group may be a chain hydrocarbon group or a cyclic hydrocarbon group. The chain hydrocarbon group may be linear or branched. Examples of the hydrocarbon group include an alkylene group, an alkenylene group, and an arylene group. The imino group and the hydrocarbon group may have a substituent.

  The linking group R may or may not contain one or more bonds selected from an ether bond, an ester bond, an amide bond and a urethane bond in the molecular chain. The amide bond includes a carboxylic acid amide bond and a sulfonamide bond. The ester bond includes a carboxylic acid ester bond, a sulfonic acid ester bond, and a phosphate ester bond.

Moreover, in said formula (3) or said formula (4), X is any one hydrophilicity imparting group selected from the group which consists of an anionic type, a cationic type, and an amphoteric type.
Examples of the anionic, cationic, and amphoteric hydrophilic imparting groups are the same as those exemplified for the linear (or branched) fluorine-based compound.

[Binder]
In the oil / water separation filter used in the present embodiment, the oil / water separator may be bonded to the substrate with a binder in order to allow the oil / water separator to stably exist on the surface of the substrate. As the binder, one or both of an organic binder (resin) and an inorganic binder (inorganic glass) can be used.

  As the organic binder (resin), a thermoplastic resin, a thermoplastic elastomer, a thermosetting resin, a UV curable resin, or the like can be used. Specific examples of the organic binder include polyvinyl chloride, polyethylene, polypropylene, polycarbonate, polyester, polystyrene, silicone resin, polyvinyl acetal, polyvinyl alcohol, acrylic polyol resin, polyester polyol resin, urethane resin, fluororesin, and thermoplastic resin. Thermosetting resins such as thermoplastic resins such as acrylic resins, epoxy resins, phenol resins, thermosetting acrylic resins, and the like can be given.

  A hydrophilic polymer can be used as the organic binder. As the hydrophilic polymer, those containing a hydroxyl group are preferred. Specific examples of the hydrophilic polymer include polysaccharides such as polyvinyl alcohol, polyvinyl butyral, cellulose, and derivatives thereof. These may be used alone or in combination of two or more. The hydrophilic polymer may be crosslinked with a crosslinking agent. By cross-linking the hydrophilic polymer (organic binder), the bond between the oil / water separator and the substrate is strengthened.

  The crosslinking agent is not particularly limited and can be appropriately selected depending on the purpose. Specific examples of the crosslinking agent include epoxy compounds, isocyanate compounds, aldehyde compounds, ultraviolet crosslinking compounds, leaving group-containing compounds, carboxylic acid compounds, urea compounds, and the like.

Specifically, as the inorganic binder (inorganic glass), for example, trialkoxysilane represented by the chemical formula [R ¹⁴ Si (OR ¹⁵ ) ₃ ], chemical formula [Si (OR ¹⁶ ) ₄ ] (R ^{14 to} R ¹⁶ And silane compounds such as tetraalkoxysilane, water glass and the like, each of which is an independent alkyl group having 1 to 6 carbon atoms. Among these, water glass is preferable because the effect of improving durability is high.

  The oil / water separator may be composed of only a fluorine-based compound having an oil repellency-imparting group and a hydrophilicity-imparting group, or may contain a binder. When a binder is included, the mass composition ratio of the fluorine-based compound and the binder is preferably in the range of 0.1 to 99.9 to 99.9 to 0.1, more preferably 2 to 98. 98 to 2, more preferably 10 to 90 to 90 to 10. Here, it is preferable that the mass composition ratio of the fluorine-based compound is 0.1 or more because sufficient hydrophilic oil repellency can be obtained. In consideration of the binding property to the substrate and the durability of the fluorine compound, the mass composition ratio of the fluorine compound and the binder is particularly preferably 10 to 90 to 90 to 10.

  The oil / water separation filter may contain chemicals such as a fungicide, an antibacterial agent and a bactericide. These chemical | medical agents may be added to the base material of the oil-water separation filter, and may be added to the oil-water separator.

[Oil-water separation filter manufacturing method]
The oil / water separation filter can be produced, for example, by applying a coating liquid containing a fluorine-based compound on the surface of a substrate and drying it.

  As the coating solution, a solution obtained by dissolving or dispersing a fluorine-based compound in a solvent can be used. The coating solution preferably contains the above-described binder. As a solvent for the coating solution, water, an organic solvent, or a mixture of water and an organic solvent can be used. Examples of the organic solvent include methanol, ethanol, IPA, tetrahydrofuran, hexane, chloroform, toluene, ethyl acetate, DMSO, DMF, acetone, a fluorine-based solvent, and the like. In particular, water, alcohols such as methanol, ethanol, and IPA, or a mixture of water and alcohols are preferable from the viewpoint of easy drying and use, and environmental impact. The mass composition ratio of the fluorine-based compound and the solvent in the coating solution is preferably from 0.01 to 5.0 to 99.99 to 95.0. If the mass composition ratio of the fluorine-based compound in the coating solution is less than 0.01, the entire substrate may not be sufficiently hydrophilic and oil-repellent, which is not preferable. On the other hand, if the mass composition ratio of the fluorine-based compound in the coating solution exceeds 95.0, the fluorine-based compound closes the pores of the base material, and the air permeability of the resulting oil / water separation filter is greatly reduced. This is not preferable because the passing speed may be too low. In consideration of the coating property and the durability of the product, the mass composition ratio of the fluorine-based compound and the solvent in the coating solution is preferably 0.1 to 5.0 to 99.9 to 95.0.

  As a method for applying the coating liquid to the surface of the porous body, a method such as a dipping method, a spray method, a printing method, a roller method, or the like can be used. Agents such as fungicides, antibacterial agents, and bactericides may be added to the coating solution to impart hydrophilic oil repellency to the porous body, and to impart antifungal and antibacterial properties.

  According to the cleaning apparatus 10 of the first embodiment described above, the oil 3 in the oil-containing water 5 generated in the cleaning tank 12 is aggregated by the oil aggregation unit 16 and then aggregated by the oil / water separation unit 17 to be coarse. Since the separated oil 3a and water 4 are separated, the oil and water in the oil-containing water 5 can be separated efficiently. Further, the oil / water separation filter used in the oil / water separation unit 17 includes an oil / water separator containing a fluorine-based compound having an oil repellency imparting group and a hydrophilicity imparting group, and has high hydrophilic oil repellency. Oil is difficult to mix. For this reason, even if it uses the isolate | separated water | moisture content as a raw material of a washing | cleaning liquid, the oil of a washing | cleaning target object can be removed stably stably over a long period of time.

<Second embodiment>
FIG. 6 is a configuration diagram showing the configuration of the cleaning device in the second embodiment. In FIG. 6, the same reference numerals are given to the same aspects as those in the first embodiment, and the description thereof is omitted.
In the cleaning device 70 according to the present embodiment, a filter 71 is provided between the cleaning tank 12 and the oil aggregation unit 16. Further, a solid particle return pipe 73 having a pump 74 is connected to the pipe 18 via a valve 72. The above points are different from the cleaning device 10 of the first embodiment.

  The filter 71 separates and removes solid particle components contained in the oil-containing water. A wire mesh can be used as the filter 71. When solid particle components such as metal pieces are mixed in the oil-containing water 5 generated in the cleaning tank 12, the oil is separated and removed by the filter 71. Further, when the solid particle component is mixed into the water separated by the oil / water separation unit 17, the solid particle return pipe 73 returns the water mixed with the solid particle component to the filter 71 to separate and remove the solid particle component. it can.

  According to the cleaning device 70 of the second embodiment described above, it is difficult for moisture mixed with solid particle components such as metal pieces to be transferred to the cleaning liquid preparation unit 11. For this reason, even if it wash | cleans continuously over a long period of time, it will become difficult to damage the washing | cleaning target object 1 by mixing of a solid particle component.

<Third embodiment>
FIG. 7 is a configuration diagram showing the configuration of the cleaning device in the third embodiment.
In FIG. 7, the same reference numerals are given to the same aspects as those in the first embodiment, and the description thereof is omitted.
In the cleaning device 80 according to the present embodiment, the cleaning tank 82 is connected to the mesh container 83 that stores the cleaning target object 1, the cleaning liquid preparation unit 11, the injector 84 that sprays the cleaning liquid 2, and the cleaning target object 1. It has the drain 85 of the oil containing water produced | generated by making it contact with the washing | cleaning liquid 2 and removing the oil adhering to the washing | cleaning target object 1. FIG. The oil-containing water drainage port 85 is different from the cleaning tank 12 of the cleaning device 10 of the first embodiment in that it is higher than the mesh container 83. In the cleaning tank 82 of this configuration, the oil adhering to the object to be cleaned rises along with the bubbles of the cleaning liquid 2, and the oil 3 a that has been coarsened is generated by the oil that has floated contacted and aggregated. To do. Accordingly, the cleaning tank 82 functions as an oil content aggregating part.

  According to the cleaning device 80 of the third embodiment described above, since the oil-containing water 5 containing the oil 3a coarsened in the cleaning tank 12 is generated, there is no need to separately provide an oil agglomeration part, so the device size can be made compact. can do.

[Invention Example 1]
(Synthesis of fluorine compounds)
“Synthesis of 2- [3- [perfluoro (2-methyl-3-dibutylaminopropanoyl)] aminopropyl-dimethyl-ammonium] acetate”
120 g of perfluoro (2-methyl-3-dibutylaminopropionic acid) fluoride obtained by electrolytic fluorination of methyl 2-methyl-3-dibutylaminopropionate was dissolved in a solution of 39 g of dimethylaminopropylamine in 500 ml of IPE solvent. The solution was added dropwise in an ice bath. After stirring at room temperature for 2 hours, filtration was performed, and the IPE layer of the filtrate was washed with an aqueous NaHCO ₃ solution and an aqueous NaCl solution, separated, and then washed with water. Thereafter, IPE was distilled off, and further distilled to obtain 64 g of (C ₄ F ₉ ) ₂ NCF ₂ CF (CF ₃ ) CONHC ₃ H ₆ N (CH ₃ ) ₂ as a crude product (yield 47%). ).
Next, 8 g of the obtained (C ₄ F ₉ ) ₂ NCF ₂ CF (CF ₃ ) CONHC ₃ H ₆ N (CH ₃ ) ₂ is refluxed with sodium monochloroacetate in ethanol overnight with stirring, filtered and concentrated. As a result, 9 g of a fluorine-based compound (dimethylbetaine) represented by the following formula (5) was obtained (yield 99%).

(Production of oil-water separation filter)
49.0 g of 2-propanol was added to 1.0 g of the fluorine compound of the above formula (5) to dissolve the fluorine compound, and 50.0 g of pure water was further added to the resulting solution, so that the concentration of the fluorine compound was A 1% by mass coating solution was obtained. A polyester fiber / glass fiber filter having an air permeability of 1 m ³ / m ² / s and a filtration accuracy of 0.5 μm is immersed in the obtained coating solution for 1 minute, and then the filter is lifted from the coating solution and applied to the filter. Was attached. The filter to which the coating solution was attached was dried at room temperature for 30 minutes, and then dried at a temperature of 80 ° C. for 1 hour to obtain a filter in which an oil / water separator was formed. The obtained filter was folded, and both ends of the folded filter were thermally welded to obtain a cylindrical oil-water separation filter.

(Production of cleaning equipment)
2 is prepared as the oil aggregation unit 16 and the oil / water separation device 60 illustrated in FIG. 5 is prepared as the oil / water separation unit 17, and the drain port 15 of the washing tank 12 and the oil aggregation device 30 are prepared. 1 is connected, the drain port 31b of the oil aggregating device 30 is connected to the inlet 62a of the oil / water separator 60, the water outlet 62b of the oil / water separator 60 is connected to the cleaning liquid preparation unit 11, and FIG. The cleaning device 10 shown in FIG. As the oil / water separation filter 65 of the oil / water separator 60, the oil / water separation filter produced as described above was used.

(Evaluation)
10 objects to be cleaned (oil adhesion amount before cleaning: 1 g / piece) were left in a cleaning tank, and the cleaning liquid was sprayed onto the object to be cleaned to clean the object to be cleaned. The cleaning time was 10 minutes, the object to be cleaned after completion of the cleaning was taken out of the cleaning tank, and the new object to be cleaned was allowed to stand in the cleaning tank. This operation was repeated 18 times. The object to be cleaned removed from the cleaning tank was dried.

After 10 minutes from the start of cleaning (after 1 operation), 1 hour (after 6 operations), 3 hours (after 18 operations), the amount of oil adhering after cleaning of the object to be cleaned removed from the cleaning tank The oil removal rate was calculated from the following equation. The results are shown in Table 1.
Oil removal rate (% by mass) = (Oil adhesion amount before washing−Oil adhesion amount before washing) / Oil adhesion amount before washing × 100

[Comparative Example 1]
In the cleaning apparatus of Example 1 of the present invention, without using an oil / water separator, oil-containing water containing coarse oil extracted from the drain outlet of the oil aggregating apparatus was supplied to the cleaning liquid preparation unit, that is, the oil content The object to be cleaned was cleaned in the same manner as in Example 1 except that the drain port 31b of the aggregating device 30 and the cleaning liquid preparation unit 11 were connected. Then, similarly to Example 1 of the present invention, after 10 minutes from the start of washing, after 1 hour, after 3 hours, the oil adhesion amount after washing of the object to be washed taken out from the washing tank was measured, and the oil removal rate was calculated. . The results are shown in Table 1.

In Comparative Example 1, the oil removal rate decreased with the passage of time from the start of cleaning, and decreased to 78% after 3 hours from the start of cleaning. This is because the oil and water removed from the object to be cleaned cannot be sufficiently separated from the cleaning object alone, so that the oil is gradually accumulated in the cleaning liquid and the oil removing ability of the cleaning liquid is reduced. it is conceivable that.
On the other hand, in Inventive Example 1, the oil removal rate was 99% even after 3 hours from the start of washing, and the oil removal rate did not decrease. This is because the oil content and water removed from the object to be cleaned can be sufficiently separated by using the oil content aggregator and the oil / water separator together. This is probably because the oil removal capability was maintained.

  DESCRIPTION OF SYMBOLS 1 ... Cleaning object, 2 ... Cleaning liquid, 3 ... Oil content, 3a ... Coarse oil content, 3b ... Oil film, 4 ... Moisture, 5 ... Oil-containing water, 10 ... Cleaning apparatus, 11 ... Cleaning liquid preparation part, 12 ... Cleaning tank , 13 ... Reticulated container, 14 ... Injector, 15 ... Drain port, 16 ... Oil condensing part, 17 ... Oil / water separating part, 18 ... Pipe, 19 ... Valve, 20 ... Oil return pipe, 21 ... Pump, 22 ... Valve, DESCRIPTION OF SYMBOLS 23 ... Extraction piping, 24 ... Piping, 25 ... Pump, 30 ... Oil content aggregation apparatus (coalescer), 31 ... Housing, 31a ... Inlet, 31b ... Drain outlet, 31c ... Oil outlet, 32 ... Filter case, 32a DESCRIPTION OF SYMBOLS ... Through-hole, 33 ... Coarse grain filter, 40 ... Oil content aggregation apparatus (oil floating device), 41 ... Processing tank, 41a ... First tank, 41b ... Second tank, 41c ... Third tank, 42a, 42b ... Partition Plate, 43a ... Inlet, 43b ... Drainage port, 44 ... Dam plate, 5 DESCRIPTION OF SYMBOLS Oil / water separator 51 ... Liquid tank 51a Open surface 51b Water outlet 51c Oil drainage channel 52 Oil / water separation filter 52a Inner surface 52b Outer surface 52c Oil outlet 52e Open end, 53 ... Dispersing plate, 54 ... Support member, 55 ... Oil tank, 60 ... Oil / water separator, 61 ... Cylindrical container, 62a ... Inlet, 62b ... Water outlet, 62c ... Oil outlet, 63 ... Post, 64a 64b ... Sealing material, 65 ... Oil / water separation filter, 70 ... Cleaning device, 71 ... Filter, 72 ... Valve, 73 ... Solid particle return piping, 74 ... Pump, 80 ... Cleaning device, 82 ... Cleaning tank, 83 ... Mesh Container, 84 ... injector, 85 ... drain

Claims (8)

A cleaning device for an object to be cleaned to which oil adheres,
A cleaning liquid preparation unit that prepares a cleaning liquid containing fine bubbles by mixing water and gas;
Oil-containing water that is a mixture of the oil and the cleaning liquid, connected to the cleaning liquid preparation unit, contacting the cleaning target and the cleaning liquid to remove the oil adhering to the cleaning target A washing tank for generating
An oil agglomeration part connected to the washing tank and agglomerating and coarsening the oil in the oil-containing water;
An oil / water separator that is connected to the oil agglomeration part and separates the oil and water from the oil-containing water containing the coarsened oil by an oil / water separator formed by forming an oil / water separator having hydrophilic oil repellency on a base material. When,
A pipe for connecting the oil / water separator and the cleaning liquid preparation section, and transferring the water separated by the oil / water separator to the cleaning liquid preparation section,
The oil / water separator includes a fluorine-based compound having an oil repellency-imparting group and a hydrophilicity-imparting group. The cleaning apparatus according to claim 1, wherein the fluorine-based compound includes one or more of compounds having a structure represented by the following formulas (1) to (4).

In the above formulas (1) and (2), Rf ¹ and Rf ² are the same or different, each having 1 to 6 carbon atoms and a linear or branched perfluoroalkyl group, and Rf ³ is carbon A number 1-6, which is a linear or branched perfluoroalkylene group;
In the above formulas (3) and (4), Rf ⁴ , Rf ⁵ and Rf ⁶ are the same or different, each having 1 to 6 carbon atoms and a linear or branched perfluoroalkylene group, and Z is Any one of an oxygen atom, a nitrogen atom, a CF ₂ group and a CF group;
In the above formulas (2) and (4), R is a linking group that is a divalent organic group;
Moreover, in said formula (1)-(4), X is any one hydrophilicity imparting group selected from the group which consists of an anionic type, a cationic type, and an amphoteric type.   The cleaning apparatus according to claim 1 or 2, wherein the oil / water separator is bonded to the base material by at least one of an organic binder and an inorganic binder, or both.   The cleaning apparatus according to any one of claims 1 to 3, wherein the base material is made of a porous body that can transmit at least moisture.   The cleaning apparatus according to claim 1, wherein the oil aggregation unit is a coalescer.   The cleaning apparatus according to any one of claims 1 to 4, wherein the oil content aggregation portion is an oil floating device.   Furthermore, it connects to the said oil-water separation part and the said oil content aggregation part, The piping which transfers the said water | moisture content isolate | separated in the said oil-water separation part to the said oil content aggregation part is provided. Cleaning equipment.   Furthermore, the washing | cleaning apparatus as described in any one of Claim 1 thru | or 7 provided with piping which returns the said water | moisture content isolate | separated in the said oil-water separation part to the said oil-water separation part.

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