JP6721989B2 - Cleaning agent for supercritical fluid processing apparatus and apparatus cleaning method using the same - Google Patents

Description

The present invention relates to a cleaning device used for cleaning a device when a dyeing dye or a functional processing type is switched in a processing device that performs a dyeing processing or a functional processing on a textile product using a supercritical carbon dioxide fluid (scCO ₂ ). The present invention relates to an agent and a method for cleaning an apparatus using the agent.

The method of coloring textile products by dyeing or adding functions by functional processing is generally performed by immersing the textile products in an aqueous solution or solvent containing a dye or a functional agent. In precious areas, it is difficult to obtain a large amount of water, and there are problems such as polluted waste water after processing and environmental destruction due to the discharge of organic solvents.In areas where environmental regulations are strict, these dyeing and processing operations are difficult. It was Therefore, a dyeing process or a functional process using a supercritical carbon dioxide fluid (scCO ₂ ) that does not use a large amount of water or a solvent has been attracting attention.

The carbon dioxide fluid in the supercritical state has properties as an excellent solvent itself, can be used as a substitute for a solvent such as water or an organic solvent, and is used for various analysis, extraction, reaction, washing and the like. Its applications cover a wide range such as various cleaning (cleaning) work, extraction work, plating process and dyeing process. As a dyeing process method of the textile product, for example, a dye is dissolved in a supercritical carbon dioxide fluid and used. There is a dyeing device (see Patent Documents 1 and 2).

Also, as a method for functionally processing a textile product, for example, a method for treating a hydrophilic fiber or a textile product using supercritical carbon dioxide as a medium and an aqueous fiber treatment agent (Patent Document 3). ) Etc.

By the way, in the dyeing process and the functional process using the supercritical carbon dioxide fluid in the above-mentioned solvent, when the color of the dyeing of the product is changed or when the process type is switched, it is the residue in the previous process from the processing tank in advance. It is necessary to remove by-products such as residual dyes, processing agents and polyester oligomers.

Here, although the supercritical carbon dioxide fluid is excellent as a solvent, it was difficult to easily dissolve the dye or other chemicals once attached inside the apparatus.

Conventionally, in a factory where a supercritical carbon dioxide fluid treatment device has been introduced and fiber dyeing processing has been put into practical use, when cleaning the dyeing kettle, residues of processing agents such as dyes and polyester oligomers from the processing tank are used. In order to remove the by-product of (1), the inside of the device was once opened, and the inside was wiped and cleaned manually.

Further, as a cleaning method performed without decomposing the inside of the apparatus, the supercritical carbon dioxide fluid that does not contain a dye or the like is overflowed for cleaning, or a cleaning agent is added to the supercritical carbon dioxide fluid for overflow cleaning. Alternatively, the unprocessed fiber is subjected to a supercritical carbon dioxide fluid treatment to exhaust the residue in the unprocessed fiber.

JP-A-2002-129464 JP, 2005-273098, A JP, 2004-076190, A

As described above, in a processing device that performs dyeing processing and functional processing using a supercritical carbon dioxide fluid, when changing the color of the dyeing on the product or switching the processing type, manual cleaning or supercritical dioxide is performed. There has been adopted a method of exhausting the residue by cleaning the carbon fluid alone or by adding a cleaning agent thereto and causing it to overflow, or performing a supercritical carbon dioxide fluid treatment on an unprocessed fiber.

However, the above-mentioned manual wipe cleaning is very inefficient because it takes time and effort to disassemble the device and reassemble or wipe it, and also any method of refluxing supercritical carbon dioxide fluid for cleaning The degree is not sufficient, and it is often inadequate unless the number of times of washing is increased or the washing time is taken long, resulting in poor efficiency and washability and high washing cost, which is a problem.

By the way, in addition to the dyeing and functional processing methods described above, it is also possible to apply the cleaning technology used for the cleaning method using a supercritical carbon dioxide fluid to the cleaning of the dyeing/processing apparatus. Many of the solvents used for cleaning are fluorine-containing solvents, such as fluorinated hydrocarbons, which can damage the Teflon (registered trademark) packing of the equipment and, in consideration of future environmental problems, cannot be used continuously. was there.

Further, in the method of applying the cleaning technology using the above-mentioned supercritical carbon dioxide fluid, it may not be suitable for cleaning highly adsorptive compounds such as dyes and fiber processing agents even though it can deal with oil stains and the like. Was known.

The present invention is to solve the above problems, a cleaning agent for a supercritical fluid processing apparatus and a cleaning method using the same, more specifically, a dyeing process for fibers using a supercritical carbon dioxide fluid as a solvent. Provide a cleaning agent that is very effective in removing residual dyes, processing agents, and by-products such as polyester oligomers from the processing tank when changing the color of the processing tank or the type of processing in functional processing and a cleaning method using the same To do.

In order to solve the above-mentioned problems, the invention of claim 1 provides the inside of a processing tank of a supercritical fluid processing apparatus for performing dyeing processing or functional processing of fibers using a supercritical carbon dioxide fluid or inside a passage of a fluid. A cleaning agent used for cleaning,
A hydrophilic part having ethylene oxide, propylene oxide, butylene oxide as a unit unit, a polymer having a molecular weight of 1,000 to 20,000, or a sugar chain compound having a molecular weight of 1,000 to 20,000;
Hydrocarbon chain or a phenyl group in this part of the carbon atoms 8 to 20, possess a hydrophobic part having a compound including naphthyl group, used in addition to the supercritical, subcritical or subcritical carbon dioxide fluid It is a cleaning agent.

The invention according to claim 2 is a cleaning agent used for cleaning the inside of a processing tank of a supercritical fluid processing apparatus that performs dyeing processing or functional processing on a fiber using a supercritical carbon dioxide fluid, or the inside of a passage of a fluid,
Phenyl or naphthyl group with ethylene oxide, propylene oxide, molecular weight of the basic unit of carbon hydrogen chains of butylene oxide or a C 8 to 20 have a polymeric adsorbent comprising a 20,000 or more polymeric compounds, ultra It is a cleaning agent to be used in a state where a critical, subcritical or subcritical carbon dioxide fluid is refluxed or left standing and arranged in a convective fluid path .

According to the invention of claim 3, a supercritical, subcritical, or subcritical carbon dioxide fluid containing the cleaning agent according to claim 1 is refluxed or left to stand to convect the carbon dioxide fluid inside the treatment tank or This is a method for cleaning a supercritical fluid processing apparatus, in which dirt components such as deposits inside the fluid path are dissolved and cleaned.

The invention according to claim 4 is a supercritical, subcritical or subcritical carbon dioxide fluid in the state where the cleaning agent (polymer adsorbent) according to claim 2 is arranged in a fluid path of a supercritical fluid processing apparatus. Is refluxed or allowed to stand to convection to dissolve the dirt components such as deposits inside the processing tank or the fluid path in the carbon dioxide fluid, and the dirt components contained in the carbon dioxide fluid are adsorbed to the cleaning agent. It is a method for cleaning a supercritical fluid processing apparatus.

The invention of claim 5 is a supercritical, subcritical or non-critical solution containing the cleaning agent of claim 1 in a state where the cleaning agent of claim 2 is arranged in a fluid path of a supercritical fluid processing apparatus. The critical carbon dioxide fluid is refluxed or allowed to stand still to cause convection to dissolve dirt components such as deposits inside the treatment tank or fluid path in the carbon dioxide fluid, and to remove the dirt components contained in the carbon dioxide fluid as described above. A method for cleaning a supercritical fluid processing apparatus, which comprises cleaning by adsorbing to the cleaning agent according to claim 2.

The cleaning agent according to claim 1 used for cleaning is required to have a property of assisting the components (substances) adhering to the pipes of the apparatus and the wall surfaces of the can body, the processing tank, etc. to dissolve in carbon dioxide. For that purpose, it has an affinity for stain components such as dyes, polyester oligomers, oils, etc., has solubility in carbon dioxide fluid, further supercritical carbon dioxide fluid, and has a characteristic that stain components cannot be reattached. It becomes a condition.

The polymer absorbent according to claim 2 used for washing has a high affinity for the dissolved disperse dye, polyester oligomer and oil component, does not melt into a carbon dioxide fluid under washing conditions, and is relatively low. It is characterized by having solubility.

Based on this feature, after being dissolved in the carbon dioxide fluid by the above cleaning agent, it plays a role of adsorbing dirt components and ensuring the solubility of dyes etc. in the carbon dioxide, and at the same time, the can body and treatment of the device. Prevents redeposition of dyes and the like on tanks and pipes, and allows the adsorbed dirt components to be collected together with the polymer adsorbent.

The cleaning agents of claims 1 and 2 are used alone as long as the cleaning effect is maintained, but by using both of them together, the cleaning effect can be maximized.

By using the cleaning agent according to claim 1 or 2, the carbon dioxide fluid is refluxed or allowed to stand and convection to cause residue on dyeing or functional processing, such as residue on the wall of the vessel or fluid passage of the apparatus. Byproducts such as dyes, processing agents, and polyester oligomers can be dissolved in a carbon dioxide fluid and removed (claims 3 to 5).

The carbon dioxide fluid used in the cleaning method according to claims 3 to 5 is preferably a supercritical carbon dioxide fluid used in dyeing processing, functional processing, etc., but is not necessarily in a supercritical state, It is also possible to use a critical or subcritical carbon dioxide fluid.

Further, at the time of cleaning, the carbon dioxide fluid may be circulated in the fluid passage to be circulated in the same manner as in the dyeing processing or the functional processing, but the carbon dioxide fluid is allowed to stand without being circulated. Even if it is made to convection, a cleaning effect is produced.

The object to be cleaned by the cleaning method of the present invention is the inner wall surface of the processing tank that is subjected to dyeing processing or functional processing in the supercritical fluid processing apparatus, the fluid passage in the fluid path through which the carbon dioxide fluid passes, the dissolution of dyes, etc. It is the inner wall surface of each part such as the tank and the circulation pump.

As described above, by performing the cleaning method of the invention of claim 3 by using the cleaning agent of the invention of claim 1, due to the circulation of carbon dioxide fluid and the convection in the stationary state, Residues from dyeing and functional processing that adhere to the wall surface, such as residual dyes and processing agents, or contaminants such as byproducts such as polyester oligomers, can be dissolved in a carbon dioxide fluid containing this cleaning agent to be efficiently removed. Therefore, when the color type or type such as the disperse dye or the functional processing is switched, it does not take time and trouble to disassemble the device for cleaning the device.

Furthermore, compared with the conventional method of circulating a supercritical carbon dioxide fluid containing a cleaning agent, the cleaning efficiency is dramatically improved, the time for switching dyeing dyes and functional processing types is shortened, and the processing cost and efficiency are improved. Improve dramatically.

Further, by performing the cleaning method of the invention of claim 4 using the cleaning agent of the invention of claim 2, the dirt component of the device dissolved in the carbon dioxide fluid by the circulation of the carbon dioxide fluid or the convection in the stationary state. Can be efficiently adsorbed and removed, and the time and labor for disassembling the device for cleaning the device are not required when switching the color type or type of the disperse dye or functional processing.

In addition, by carrying out the cleaning method of the invention of claim 5 by using the cleaning agent of the invention of claim 1 in combination with the cleaning agent of the invention of claim 2, the cleaning effect is further improved.

It is a schematic diagram which shows the whole supercritical fluid processing apparatus which concerns on this invention. It is a schematic diagram of the principal part at the time of cleaning a supercritical fluid processing apparatus using the cleaning agent of the present invention.

(A) Molecular structure of detergent (surfactant) and its characteristics The detergent according to claim 1 of the present invention is a surfactant having an amphipathic molecular structure, and has a hydrophilic part and a hydrophobic part as a basic skeleton. Although it has, as the hydrophilic part, a polymer having a molecular weight of 1,000 to 20,000 or a molecular weight of 1,000 to 20,000, which has ethylene oxide (EO), propylene oxide (PO), or butylene oxide (BO) as a unit unit. It is a 20,000 sugar chain compound.

On the other hand, the hydrophobic portion is a hydrocarbon chain having 8 to 20 carbon atoms, or a compound having a phenyl group or a naphthyl group in a part thereof.

Since the dirt component such as dye and the carbon dioxide fluid are both hydrophobic, the function of the cleaning agent required in the present invention is different from that required for the surfactant when water is used as a medium, but the cleaning is performed. For the sake of convenience in expressing the structure of the agent, the term "surfactant" will be used for description.
[Chemical formula 1] shows an example of the chemical structure.

In the chemical structural formula [Chemical formula 1], the detergent of the present invention may not have a carboxyl group (—COOH) at the terminal of the hydrophobic portion.

Further, as other constituent elements, cationic surfactants such as dialkyldimethylammonium salt and N-(3-octadecanoylaminepropyl)-N-2-octadecanoyloxyethyl)N-(methylammonium) salt , Double-sided surfactants such as alkyl imidazolium salts, and cyclic polypeptides.

(B) Molecular structure of cleaning agent (polymer adsorbent) and its characteristics As a molecular structure of the cleaning agent (polymer adsorbent) according to claim 2 of the present invention, a phenyl group or a naphthyl group, ethylene oxide, Examples of the polymer compound include propylene oxide, butylene oxide, or a polymer compound having a carbon-hydrogen chain having 8 to 20 carbon atoms as a unit unit and having a molecular weight of 20,000 or more. Examples of these polymer adsorbents are shown in [Chemical Formula 2].

Next, a method for cleaning a supercritical fluid processing apparatus using the above-described cleaning agent of the present invention will be described with reference to the accompanying drawings.

FIG. 1 is a schematic diagram showing the basic configuration of a supercritical fluid processing apparatus that performs dyeing processing and functional processing on fibers using a supercritical carbon dioxide fluid. The dissolution tank 2 and the can body 3 into which the fiber is charged are connected by a circulation passage 4 via a filter or the like (not shown), and the circulation pump 5 causes the supercritical carbon dioxide fluid 6 to dissolve the dye or the like. 2 and the can body 3 are circulated, and the processing tank 7 in the can body 3 uses a supercritical carbon dioxide fluid 6 as a solvent to perform dyeing processing and functional processing on fibers.

However, in the circulation pump 5, the carbon dioxide fluid does not pass through the inside of the rotating body such as the motor, and the fluid is circulated by indirectly transmitting the rotation of the motor or the like to the mechanism for delivering the fluid in the circulation path. Including type.

Reference numeral 10 is a filter unit 10 for storing a cleaning agent made of a polymer adsorbent described later. The arrangement of the dissolution tank 2 for dye or the like, the can body 3, the circulation pump 5, and the filter portion 10 in the circulation passage 4 shown in FIG. 1 is an example, and the arrangement is not limited to these, and the same action and effect can be obtained. The design is appropriately changed within the range of possession.

FIG. 2 shows that, for the supercritical fluid processing apparatus 1, two kinds of cleaning agents 8 (surfactant) and cleaning agent 9 (polymer adsorbent) are used together when changing colors or processing types. It is the schematic diagram which expanded the principal part which shows the state which wash|cleans the inside.

The cleaning agent 8 (surfactant) is introduced by an appropriate means in the same manner as in the case of adding a dye or a functionally processed product at the time of processing, so that the dye or the like disposed on the way of the circulation passage 4 shown in FIG. 1 is dissolved. The cleaning agent 9 (polymer adsorbent) may be charged into the tank 2 or the like, and the cleaning agent 9 (polymer adsorbent) may be appropriately added to a portion located downstream of the surfactant 8 for cleaning, mainly the filter portion 10 or the like according to the flow direction of the fluid. Install.

The fluid used for this washing is preferably the same as the supercritical carbon dioxide fluid 6 used for the dyeing and functional processing of the fibers, but carbon dioxide that is not subcritical or non-critical A fluid may be used, and the carbon dioxide fluid 11 is used.

At this time, the stain component S such as the residual dye increases the number of times the carbon dioxide fluid 11 comes into contact with the detergent 9 (polymer adsorbent) during circulation and increases the surface area to enhance the washing property. It may be applied to spheres such as beads, or a layered structure may be formed by using a thin glass filter carrying the cleaning agent 9, but it can be held by various known means without limitation.

Next, the carbon dioxide fluid 11 is circulated by the action of the circulation pump 5 or left standing for convection to perform a cleaning operation. The cleaning conditions are preferably a temperature of 31° C. or higher and a pressure of 7.38 MPa or higher.

The carbon dioxide fluid 11 flows in the circulation passage 4 in the direction of the arrow, and the cleaning agent 8 (surfactant) added to the carbon dioxide fluid 11 causes the treatment tank 7 in the can body 3, the dye, etc. The dirt component S adhering to the inner wall surfaces of the dissolution tank 2, the circulation passage 4 and the like is dissolved in the carbon dioxide fluid 11.

The carbon dioxide fluid 11 in which the dirt component S desorbed from the wall surface by the cleaning agent 8 (surfactant) is dissolved is sent to the filter unit 10 through the circulation passage 4, and the dirt component S is used as the cleaning agent of the present invention at this portion. A system such as a series of column chromatography in which the cleaning agent 9 (polymer adsorbent) is adsorbed is constructed.

As the carbon dioxide fluid 11 is circulated or left standing by the circulation pump 5 to be convected and the contaminated component S is dissolved by the detergent 8 (surfactant) in the carbon dioxide fluid 11, the cleaning in the filter unit 10 is performed. Adsorbed on the agent 9 (polymer adsorbent).

As the cleaning agent, the cleaning agent 8 made of the surfactant of claim 1 of the present invention and the cleaning agent 9 made of the polymer adsorbent of claim 2 of the present invention are separately used at the time of cleaning. However, it is more effective to use both of them for cleaning.

After the carbon dioxide fluid 11 is circulated or left standing for convection for a predetermined time for cleaning, carbon dioxide is discharged and the cleaning agent 9 is removed, and then the dyeing dye or the functional processing type is switched to perform the treatment. It can be carried out.

The experiment was conducted in a supercritical fluid processing device having a volume of 5 l (liter). Detergency was observed for the surfactants Brij 35, 58 and structures having an alkyl chain (C12, C22) and a PEG chain in the molecule.

In addition, when a drug included in the range of [Chemical formula 2] as a polymer adsorbent was used in conjunction with the detergent (surfactant) of the preceding paragraph, the most effective effect was observed.

As a test method, after dyeing (dark color) the fiber, the amount of dye remaining in the can body of the apparatus was measured, and the dye amount was washed in the embodiment described in the preceding paragraph. Then, the residual dye after washing was washed by using an unprocessed cloth, and the color density was evaluated by K/S value.
Table 1 shows an example of the results.

* Weight Loss in Table 1 indicates the weight loss rate of the cleaning agent. A negative number means that the amount increased by adsorbing a dye or the like.

1 Supercritical Fluid Treatment 2 Melting Tank 3 Can 4 Circulation Passage 5 Circulation Pump 6 Supercritical Carbon Dioxide Fluid 7 Treatment Tank 8 Cleaning Agent (Surfactant)
9 Cleaning agent (polymer adsorbent)
10 Filter 11 Carbon dioxide fluid S Dirt component

Claims (5)

A cleaning agent used for cleaning the inside of a processing tank of a supercritical fluid processing device that performs dyeing processing or functional processing on a fiber using a supercritical carbon dioxide fluid and the inside of a passage of a fluid,
A hydrophilic part having ethylene oxide, propylene oxide, butylene oxide as a unit unit, a polymer having a molecular weight of 1,000 to 20,000, or a sugar chain compound having a molecular weight of 1,000 to 20,000;
Hydrocarbon chain or a phenyl group in this part of the carbon atoms 8 to 20, possess a hydrophobic part having a compound including naphthyl group, used in addition to the supercritical, subcritical or subcritical carbon dioxide fluid A cleaning agent for a supercritical fluid treatment device, comprising: A cleaning agent used for cleaning the inside of a processing tank of a supercritical fluid processing device that performs dyeing processing or functional processing on a fiber using a supercritical carbon dioxide fluid and the inside of a passage of a fluid,
Phenyl or naphthyl group with ethylene oxide, propylene oxide, molecular weight of the basic unit of carbon hydrogen chains of butylene oxide or a C 8 to 20 have a polymeric adsorbent comprising a 20,000 or more polymeric compounds, ultra A cleaning agent for a supercritical fluid treatment device, characterized in that it is used in a state where a critical, subcritical, or subcritical carbon dioxide fluid is refluxed or left standing and arranged in a convective fluid path . A supercritical, subcritical, or subcritical carbon dioxide fluid containing the cleaning agent according to claim 1 is refluxed or left to stand to convect, and the carbon dioxide fluid is deposited on the inside of the treatment tank or the fluid path. A method for cleaning a supercritical fluid treatment device, characterized in that dirt components such as are dissolved and cleaned. In a state where the cleaning agent according to claim 2 is arranged in the fluid path of the supercritical fluid processing apparatus, the supercritical, subcritical or subcritical carbon dioxide fluid is refluxed or left to stand to convection, A supercritical fluid treatment characterized by dissolving dirt components such as deposits inside the treatment tank or fluid path in a carbon fluid and adsorbing the dirt components contained in the carbon dioxide fluid to the cleaning agent for cleaning. How to clean the equipment. The supercritical, subcritical or subcritical carbon dioxide fluid containing the cleaning agent according to claim 1 is refluxed in a state where the cleaning agent according to claim 2 is arranged in the fluid path of the supercritical fluid processing apparatus. Alternatively, the contaminated components contained in the carbon dioxide fluid may be cleaned by allowing the carbon dioxide fluid to dissolve contaminated components such as deposits inside the treatment tank or the fluid path by convection by standing still. A method for cleaning a supercritical fluid processing apparatus, which comprises adsorbing to an agent and cleaning.

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