WO2025257751A1 - Method of manufacturing functionalized base material, functionalized base material, and apparatus for manufacturing functionalized base material - Google Patents

Method of manufacturing functionalized base material, functionalized base material, and apparatus for manufacturing functionalized base material

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Publication number
WO2025257751A1
WO2025257751A1 PCT/IB2025/055965 IB2025055965W WO2025257751A1 WO 2025257751 A1 WO2025257751 A1 WO 2025257751A1 IB 2025055965 W IB2025055965 W IB 2025055965W WO 2025257751 A1 WO2025257751 A1 WO 2025257751A1
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WO
WIPO (PCT)
Prior art keywords
base material
functionalizing agent
functionalized
functionalized base
oligomers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/IB2025/055965
Other languages
French (fr)
Inventor
Yuuki Gotoh
Daisuke Asahina
Hideo Nakamori
Hideaki Nishimura
Satoshi Shinohara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ricoh Co Ltd
Original Assignee
Ricoh Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ricoh Co Ltd filed Critical Ricoh Co Ltd
Publication of WO2025257751A1 publication Critical patent/WO2025257751A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/94—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dyes dissolved in solvents which are in the supercritical state
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • D06M23/105—Processes in which the solvent is in a supercritical state

Definitions

  • the present disclosure relates to a method of manufacturing a functionalized base material, a functionalized base material, and an apparatus for manufacturing a functionalized base material.
  • a method for treating a molded resin body has been reported as a batch-type waterless dyeing method.
  • a supercritical fluid in which a colorant or a functional agent, or both a colorant and a functional agent, are dissolved is contacted with the molded resin body containing an additive.
  • the additive is extracted from the molded resin body, and the colorant or the functional agent, or both the colorant and the functional agent, are applied to a surface layer of the molded resin body (see, for example, PTL 1).
  • a method for imparting a function to a polymeric molded product has been reported as a continuous waterless dyeing method.
  • a supercritical fluid is sprayed onto a polymeric molded product and a functionalizing agent is fixed to the polymeric molded product (see, for example, PTL 2).
  • An object of the present disclosure is to provide a method of manufacturing a functionalized base material in which no chemicals such as surfactants or large amounts of water are used, and by which surface contamination of fibers due to elution of oligomers and deposition of the eluted oligomers inside an apparatus can be reduced.
  • a functionalizing agent can be adsorbed inside a base material or uniformly attached to the surface of the base material and diffused into the base material.
  • the method can use a continuous process and control the amount of the functionalizing agent applied to each discharge site, so that differentiated dyeing and image formation can be implemented with a plurality of types of functionalizing agents.
  • Embodiments of the present disclosure provide a method of manufacturing a functionalized base material.
  • the method includes discharging and applying to a base material a supercritical fluid in a gas phase state or a supercritical state in which the functionalizing agent is dissolved.
  • a method of manufacturing a functionalized base material can be provided in which no chemicals such as surfactants or large amounts of water are used, and by which surface contamination of fibers due to elution of oligomers and deposition of the eluted oligomers inside an apparatus can be reduced.
  • a functionalizing agent can be adsorbed inside a base material or uniformly attached to the surface of the base material and diffused into the base material.
  • the method can use a continuous process and control the amount of the functionalizing agent applied to each application site, so that differentiated dyeing and image formation can be implemented with a plurality of types of functionalizing agents.
  • FIG. 1 is a schematic diagram illustrating an apparatus for manufacturing a functionalized base material.
  • FIG. 2 is a cross-sectional view of a pulse valve in an apparatus for manufacturing a functionalized base material.
  • FIG. 3 is a partial cross-sectional view of the pulse valve illustrated in FIG. 2.
  • FIG. 4 is a cross-sectional view of a pulse valve in an apparatus for manufacturing a functionalized base material.
  • FIG. 5 is a cross-sectional view of the pulse valve taken along line A-A in FIG. 4.
  • FIG. 6 is a spectrum derived from a surfactant in a functionalized base material of Comparative Example 3.
  • FIG. 7 is a spectrum of a surfactant.
  • the accompanying drawings are intended to depict embodiments of the present disclosure and should not be interpreted to limit the scope thereof. The accompanying drawings are not to be considered as drawn to scale unless explicitly noted. Also, identical or similar reference numerals designate identical or similar components throughout the several views. [Description of Embodiments]
  • a method of manufacturing a functionalized base material of the present embodiment is a method of manufacturing a functionalized base material having a base material and a functionalizing agent, and includes a step of discharging and applying to the base material a supercritical fluid in a gas phase state or a supercritical state in which the functionalizing agent is dissolved (i.e., application step), and further includes other steps, if desired.
  • the method of manufacturing a functionalized base material can be suitably implemented by an apparatus for manufacturing a functionalized base material of the present embodiment, which will be described later.
  • the present disclosure responds to the following issues found by the inventors of the present invention.
  • oligomers contained in fibers are eluted onto the surface of the fibers and accumulate in the batch, and in addition, the eluted oligomers reattach to the fibers, so that uniform dyeing properties deteriorate.
  • the size of the fibers or fabric is limited to a size that can be stored in a batch container, the fabric has to be cut for each batch, and all of the fibers or fabric have to be dyed for each batch.
  • a reactor including a gap having substantially an inverted T-shape in its cross-sectional view is used, and a functional material liquid and supercritical carbon dioxide are mixed in a mixing coil and sprayed onto a polymeric molded product such as a fiber that is moved through the gap.
  • a part of the functional material that does not completely dissolve in the supercritical carbon dioxide is sprayed as a liquid, and thus, it is difficult to apply the functional material uniformly or locally onto the fiber, and it is difficult to control the amount of the functional material to be applied.
  • the inventors of the present invention have found the following. That is, by providing a step of discharging and applying to the base material a supercritical fluid that contains the functionalizing agent and is in a gas phase state and/or a supercritical state, it is possible to reduce contamination of the surface of the fibers due to the elution of oligomers and deposition of eluted oligomers within the apparatus, without using chemicals such as surfactants or a large amount of water. Further, it is possible to adsorb the functionalizing agent inside the base material or to cause the functionalizing agent to uniformly adhere to the surface of the base material to diffuse the functionalizing agent inside the base material. It is possible to use a continuous process and control the amount of the functionalizing agent applied to each application site, so that differentiated dyeing and image formation can be implemented with a plurality of types of functionalizing agents.
  • the application step is a step of discharging and applying to the base material a supercritical fluid that contains the functionalizing agent and is in a gas phase state or a supercritical state.
  • the application step can be suitably implemented by using a high-pressure vessel and a pulse valve in an apparatus for manufacturing a functionalized base material of the present embodiment, which will be described later.
  • the discharged supercritical fluid does not include a liquid phase.
  • the temperature and the pressure of a high-pressure vessel are controlled and the supercritical fluid is sprayed onto a polymer structure body from a nozzle unit so that the supercritical fluid or a mixture of the supercritical fluid and an entrainer does not transition from the supercritical state to a liquid state or a solid state when the supercritical fluid containing the functionalizing agent is discharged from the nozzle unit (that is, when the fluid expands).
  • the supercritical fluid when the supercritical fluid is a supercritical carbon dioxide fluid and does not contain an entrainer, referring to the Mollier diagram for carbon dioxide alone, the supercritical fluid can be discharged and applied in a gas phase state or a supercritical state by controlling the high- pressure vessel to achieve a temperature of 390 K (about 117 degrees) or higher at 25 MPa, and 408 K (about 135 degrees) or higher at 40 MPa.
  • the base material to which the functionalizing agent is to be applied is conveyed or a discharge position of a pulse valve or the like with respect to the base material is scanned. Therefore, the functionalizing agent can be discharged in a continuous process.
  • the amount of the functionalizing agent to be applied to each application region of the base material can be controlled, and thus, it is possible to apply the functionalizing agent to specific regions of the base material, and to implement differentiated dyeing and image formation. Specific examples of these aspects include an aspect in which the content of the functionalizing agent in a first region of the functionalized base material is different from the content of the functionalizing agent in a second region of the functionalized base material.
  • the application step may include a first application step and a second application step.
  • the functionalizing agent contains a first functionalizing agent and a second functionalizing agent.
  • a supercritical fluid in which the first functionalizing agent is dissolved is discharged and applied to the base material in a gas phase state and/or a supercritical state.
  • a supercritical fluid in which the second functionalizing agent is dissolved is discharged and applied to the base material in a gas phase state and/or a supercritical state.
  • the first functionalizing agent and the second functionalizing agent are not particularly limited and can be selected according to a purpose from functionalizing agents that are different from each other.
  • the base material is not particularly limited and can be appropriately selected according to a purpose.
  • the base material is preferably a polymeric molded body molded of a polymer.
  • the material of the polymeric molded body is not particularly limited and can be appropriately selected according to a purpose.
  • the material include, but are not limited to, polyester-based polymers such as polyethylene terephthalate (PET); polyolefin- based polymers; polyamide -based polymers such as Nylon 6; acrylate-based polymers such as polyacrylonitrile; acetate -based polymers; polyvinyl chloride-based polymers; and aramid- based polymers.
  • the polymeric molded body may be in the form of fibers such as raw yarn and twisted yarn, in the form of fabrics such as woven fabric, knitted fabric, and nonwoven fabric, or in the form of a film or a plate, and any of these shapes may be suitably applied.
  • the polymeric molded body is preferably a fabric, a film, or a plate, and more preferably a fabric, because in this case, it is possible to advantageously realize the possibility of differentiated dyeing and image formation.
  • polyester-based polymer polyethylene terephthalate is preferred.
  • the polyethylene terephthalate may contain a copolymerization component, and preferably contains 90 mol% or more of repeating units of polyethylene terephthalate, and more preferably contains 95 mol% or more of repeating units of polyethylene terephthalate.
  • the polymeric molded body may contain any copolymerization component, and may also contain additives such as stabilizers, antioxidants, antistatic agents, fluorescent whitening agents, catalysts, and colorants.
  • the supercritical fluid refers to a fluid under supercritical conditions including a temperature equal to or higher than the critical temperature and a pressure equal to or higher than the critical pressure.
  • supercritical carbon dioxide fluid refers to a carbon dioxide fluid under supercritical conditions including a temperature of 31.1 °C or higher, which is the critical temperature of carbon dioxide, and a pressure of 7.48 MPa or higher, which is the critical pressure of carbon dioxide.
  • the supercritical fluid may also be used together with an entrainer (i.e., auxiliary solvent).
  • an entrainer i.e., auxiliary solvent
  • examples of the entrainer include, but are not limited to, alcohols such as methanol, ethanol, and propanol; ketones such as acetone and methyl ethyl ketone; and organic solvents such as toluene, ethyl acetate, and tetrahydrofuran. These entrainers may be used alone or in combination of two or more types.
  • the functionalizing agent is not particularly limited and can be appropriately selected according to a purpose and the physicochemical characteristics of the base material.
  • the functionalizing agent include, but are not limited to, dyes; preservatives, antifungal agents, waterproofing agents, conductive agents, ultraviolet absorbing agents, strength enhancing agents, oxidizing agents, neutralizing agents, metals, catalyst deactivators, slipping agents, light stabilizers, anti-tack agents, lubricants, fire retardants, coupling agents, processing aids, antistatic agents, nucleating agents, and foaming agents.
  • dyes are preferred in dyeing applications, and preservatives, antifungal agents, waterproofing agents, and conductive agents are preferred in various other applications.
  • These functionalizing agents may be used alone or in combination of two or more types. Specifically, two or more types of functionalizing agents may be mixed and applied in one application step, or two or more types of functionalizing agents may be applied individually in two or more application steps.
  • the functionalizing agent is suitably selected so that the functionalizing agent does not dissolve from the functionalized base material under practical use conditions, and the functionalizing agent substantially does not dissolve or only a very small amount of the functionalizing agent dissolves in the functionalized base material and the base material under normal conditions.
  • Examples of the dyes include, but are not limited to, disperse dyes, acid dyes, acid mordant dyes, basic dyes, direct dyes, construction dyes, reactive dyes, and naphthol dyes.
  • disperse dyes are preferred, because disperse dyes have excellent solubility in the supercritical carbon dioxide fluid.
  • a dispersant is used to stably disperse the disperse dye in water.
  • the disperse dye can be mixed with a supercritical fluid and used without using a dispersant.
  • disperse dyes include, but are not limited to, Disperse Yellow 54, Disperse Yellow 122, Disperse Yellow 124, Disperse Yellow 128, Disperse Yellow 134, Disperse Yellow 140, Disperse Orange 5, Disperse Orange 25, Disperse Orange 37, Disperse Orange 93, Disperse Orange 103, Disperse Orange 112, Disperse Orange 134, Disperse Orange 370, Disperse Green 7, Disperse Violet 61, Disperse Violet 63, Disperse Brown 1, Disperse Brown 13, Disperse Blue 14, Disperse Blue 27, Disperse Blue 54, Disperse Blue 56, Disperse Blue 176, Disperse Blue 182, Disperse Blue 193, Disperse Red 60, Disperse Red 146, Disperse Red 199, Disperse Red 202, Disperse Red 204, and Disperse Red 291. These disperse dyes may be used alone or in combination of two or more types.
  • preservatives and the antifungal agents include, but are not limited to, MARUKACIDE YP-DP (manufactured by Osaka Kasei Co.), AMOLDEN HS (manufactured by Daiwa Chemical Industries Co., Ltd.), catechin, chitosan, flavone, acrylonitrile, and polyanions of which each molecule has a plurality of anionic functional groups such as carboxyl groups, sulfonic acid groups, sulfate groups, and phosphate groups.
  • waterproofing agents examples include, but are not limited to, NEOSEED (manufactured by Nicca Chemical Co., Ltd.), QUEENSET PSO-5500 (manufactured by Kotani Chemical Industry Co., Ltd.), and POLONCOAT-E (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Examples of the conductive agents include, but are not limited to, silver acetylacetonate, dimethylcyclooctadiene platinum II, and palladium bisacetylacetonate.
  • fire retardants examples include, but are not limited to, aromatic condensed phosphate esters.
  • ultraviolet absorbing agents examples include, but are not limited to, benzotriazole- based agents and benzophenone -based agents.
  • strength enhancing agents include, but are not limited to, silicone oil.
  • neutralizing agents or catalyst deactivators include, but are not limited to, zinc oxide, zinc stearate, aliphatic amines, and aliphatic amides.
  • Examples of the metals include, but are not limited to, copper, silver, nickel, and gold.
  • Examples of the slipping agents include, but are not limited to, erucamide, oleamide, and ethylene bisstearamide.
  • Examples of the light stabilizers include, but are not limited to, benzophenone -based light stabilizers.
  • anti-tack agents examples include, but are not limited to, diatomaceous earth, silica, clay, and talc.
  • lubricants include, but are not limited to, organic modified polydimethylsiloxane.
  • processing aids include, but are not limited to, calcium stearate and organic modified polydimethylsiloxane.
  • antistatic agents include, but are not limited to, glycerol monostearate, ethoxylated amines, polyethylene glycol esters, and quaternary ammonium compounds.
  • foaming agents include, but are not limited to, azodicarbonamide and sodium bicarbonate.
  • the functionalized base material of the present embodiment is a functionalized base material including a base material and a functionalizing agent.
  • the functionalized base material is substantially free of surfactants, and the content of internal oligomers is 50 mass% or more of all oligomers in the base material.
  • the base material is not particularly limited and may be appropriately selected according to a purpose from the materials mentioned above in the description of the base material in the method of manufacturing a functionalized base material of the present embodiment.
  • the shape of the base material and the functionalized base material is not particularly limited and can be appropriately selected according to a purpose.
  • the base material and the functionalized base material are preferably in the form of a fabric.
  • the functionalizing agent is not particularly limited and can be appropriately selected according to a purpose from the materials mentioned above in the description of the functionalizing agent in the method of manufacturing a functionalized base material of the present embodiment.
  • the functionalizing agent is not particularly limited and can be appropriately selected according to a purpose.
  • the functionalizing agent is preferably a dye, and in another aspect or an additional aspect, the functionalizing agent includes preferably one or more types selected from the group consisting of a preservative, an antifungal agent, a waterproofing agent, and a conductive agent.
  • the functionalized base material of the present embodiment it is possible to apply a functionalizing agent to a specific site of a base material, and to realize differentiated dyeing and image formation.
  • Specific examples of these aspects include an aspect in which the content of the functionalizing agent in a first region of the functionalized base material is different from the content of the functionalizing agent in a second region of the functionalized base material.
  • the functionalizing agent includes a plurality of functionalizing agents, for example, an aspect in which the functionalizing agent includes a first functionalizing agent and a second functionalizing agent.
  • a functionalized base material may be obtained that contains the first functionalizing agent and the second functionalizing agent in specific regions of the functionalized base material.
  • a functionalized base material may be obtained in which the content and the application pattern of the first functionalizing agent and the content and the application pattern of the second functionalizing agent are different in each region of the functionalized base material. Any of these aspects can be appropriately selected according to a purpose.
  • the content of internal oligomers is 50 mass% or more, preferably 60 mass% or more, and more preferably 70 mass% or more, of all the oligomers in the base material.
  • the content of surface oligomers is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less, of all the oligomers in the base material.
  • oligomers contained in fibers are eluted onto the surface of the fibers and accumulate in the batch, and in addition, the eluted oligomers reattach to the fibers, so that uniform dyeing properties deteriorate.
  • the content of internal oligomers decreases (that is, less than 50% of all the oligomers) and the content of the surface oligomers increases (for example, more than 50% of all the oligomers).
  • the base material is not maintained in a heated state within a batch for a long period of time as in the batch-type waterless dyeing method.
  • a supercritical fluid in which a functionalizing agent is dissolved is discharged and applied to the base material in a gas phase state and/or a supercritical state. Therefore, it is possible to control the applied amount of the supercritical fluid locally and reduce the time the base material is exposed to an atmosphere in which oligomers are easily dissolved. Therefore, according to the present embodiment, the supercritical fluid is applied under reduced pressure, and thus, the treatment time is short.
  • oligomers are less likely to be eluted from inside the base material, so that the oligomers do not remain in the batch, the loss of internal oligomers within the functionalized base material is reduced, and the elution of surface oligomers is reduced.
  • polyester fibers before dyeing contain a total amount of oligomers of about 1 mass%, and the amount of surface oligomers adhering to the surface of the polyester fibers is about 0.1 mass% (Development of a Polyester Oligomer Removal Agent: Jun Kamitani, Yasunari Sawanoi, and Hiroyuki Hasebe). As will become apparent from the Examples described later, the total oligomer content was about 1.4 mass%, and the content of surface oligomers was 0.11 mass%, which is similar to the above-mentioned report (see Comparative Example 1 in Table 1).
  • the content of the internal oligomer in the functionalized base material is preferably 0.8 mass% or more, more preferably 0.9 mass% or more, and even more preferably 1.0 mass% or more, of the functionalized base material.
  • the content of the internal oligomers in the functionalized base material can be appropriately selected in accordance with the oligomer content in the base material being used, and is preferably 60 mass% or more, more preferably 70 mass% or more, and even more preferably 80 mass% or more, of all the oligomer in the base material.
  • the content of the surface oligomers in the functionalized base material is preferably 0.7 mass% or less, more preferably 0.6 mass% or less, and even more preferably 0.5 mass% or less, of the functionalized base material.
  • the content of all oligomers in the functionalized base material can be determined by appropriately selecting a known method depending on the type of base material used.
  • the base material can be completely dissolved in a solvent that can dissolve the base material, and then, a polymer can be precipitated using an appropriate solvent.
  • the precipitated polymer can be removed by filtration to extract and quantitatively analyze all oligomers.
  • the base material is polyethylene terephthalate (PET)
  • PET polyethylene terephthalate
  • the functionalized base material is completely dissolved in hexafluoropropanol
  • the polymer is precipitated with acetonitrile, and then, the precipitate is filtered through a filter to obtain a hexafluoropropanol extract.
  • the obtained extract is analyzed by high-pressure liquid chromatography (HPLC) analysis and the oligomers are quantified to measure the oligomer content.
  • HPLC high-pressure liquid chromatography
  • a sample for analyzing the content of all oligomers can be obtained by the following procedure.
  • a functionalized base material is cut to obtain a piece having a size of 1 cm x 1 cm, which is used as an evaluation sample.
  • the evaluation sample is divided into four equal pieces, one of which is placed in a 10 ml vial, and about 0.6 ml of hexafluoropropanol is added to the vial.
  • the vial is left standing for about 2 hours, and then, about 9.4 ml of acetonitrile is added.
  • the obtained mixture is filtered through a PTFE filter having a pore size of 0.2 pm to obtain a sample for analyzing the content of all oligomers.
  • the content of surface oligomers in the functionalized base material can be determined by appropriately selecting a known method in accordance with the type of the base material being used.
  • the surface oligomers can be extracted and quantitatively analyzed by dissolving the surface of the base material in a solvent that can dissolve the surface of the base material.
  • the base material is polyethylene terephthalate (PET)
  • PET polyethylene terephthalate
  • the functionalized base material is subjected to an extraction with tetrahydrofuran, the obtained extract is analyzed by HPLC analysis and the oligomers are quantified.
  • the content of internal oligomers can be calculated by subtracting the content of surface oligomers from the content of all oligomers.
  • a sample for analyzing the content of surface oligomers can be obtained by the following procedure.
  • a part (about 0.015 g) of a functionalized base material is separated to be used as an evaluation sample.
  • the evaluation sample is placed in a 10 ml vial, and about 5 ml of THF is added to the vial.
  • the mixture is treated with ultrasonic waves at 40 KHz for 30 minutes at an initial temperature of 25°C, and then allowed to stand one night to obtain a THF extract.
  • About 9.5 ml of acetonitrile is added to 1 ml of the THF extract to obtain a sample for analyzing the surface oligomers.
  • the sample for analyzing the content of all the oligomers or the sample for analyzing the surface oligomers can be used to perform HPLC analysis under the following HPLC conditions.
  • Phase A 10 mM aqueous solution of ammonium formate
  • Phase B acetonitrile - Gradient conditions:
  • the base material is polyethylene terephthalate (PET) in a method of calculating a quantitative value from the peak area in HPLC
  • PET polyethylene terephthalate
  • CDMP dimethyl phthalate
  • a calibration curve for dimethyl phthalate is calculated from the measurement results of a standard solution of DMP.
  • a standard solution about 60 mg of dimethyl phthalate is dissolved and diluted with acetonitrile in a 50 ml measuring flask to prepare a DMP standard solution having a known concentration of 1200 ppm, which is then progressively diluted and used.
  • the content in terms of DMP is calculated from the peak area in HPLC corresponding to the oligomers. Subsequently, the content in terms of DMP is converted into the content of CDMP, assuming that the molar absorption coefficient of CDMP is three times the molar absorption coefficient of DMP.
  • the functionalized base material is substantially free of surfactants.
  • “substantially free” means that, when the functionalized base material is extracted with tetrahydrofuran (THF) and components thereof are analyzed, the content of surfactants to be evaluated is below the detection limit.
  • THF tetrahydrofuran
  • the THF extract of the functionalized base material and the sample used for analyzing the components can be obtained by the following procedure.
  • a part (about 0.01 g) of the functionalized base material is separated to be used as an evaluation sample.
  • the evaluation sample is placed in a 1.5 ml vial, and about 1.2 g of THF is added to the vial.
  • the mixture is treated with ultrasonic waves at 40 KHz for 30 minutes at an initial temperature of 25°C, and then allowed to stand one night to obtain a THF extract.
  • the obtained THF extract is diluted about 10-fold with acetonitrile and fdtered through a 0.45 pm PTFE fdter to obtain a sample for analyzing the components.
  • LC-MS analysis can be performed under the following LC-MS conditions and MS conditions, to confirm that no peak is detected for the surfactants being measured.
  • Phase A 10 mM aqueous solution of ammonium formate
  • Phase B acetonitrile
  • phase A/phase B volume ratio
  • phase A/phase B volume ratio
  • phase A/phase B volume ratio
  • the functionalized base material preferably includes the functionalizing agent inside the functionalized base material.
  • the functionalized base material “includes” the functionalizing agent “inside” the functionalized base material by, for example, evaluating the washing fastness and the rubbing fastness to confirm if the functionalizing agent such as a dye does not elute or detach from the functionalized base material.
  • the evaluation it is possible to evaluate whether a material satisfies at least any one of (1) to (3) below, and it is preferable to evaluate whether a material satisfies all of
  • a discoloration degree evaluated by a washing fastness test according to Japanese Industrial Standards (JIS) L 0844 No. A-2 is grade 4 or higher.
  • a staining degree evaluated by a washing fastness test according to JIS L 0844 No. A-2 is grade 3 or higher.
  • a staining degree evaluated by a rubbing fastness test that is a dry test according to the rubbing tester type II method (Gakushin-type method) of JIS L 0849 is grade 3 to 4 or higher.
  • JIS L 0844 No. A-2 corresponds to Test 2B(2) of the international standard ISO 105-C10
  • JIS L 0849 corresponds to the international standard ISO 105-X12, and thus, each evaluation can be performed in accordance with the corresponding standards.
  • examples of a method of evaluating whether the functionalized base material contains a functionalizing agent other than a dye therein include a method of comparing the content of the functionalizing agent in the functionalized base material after the washing test for the washing fastness with the content of the functionalizing agent in a control functionalized base material that is not subjected to the washing test; and a method of comparing the content of the functionalizing agent in the functionalized base material after the rubbing test for the rubbing fastness with the content of the functionalizing agent in a control functionalized base material that is not subjected to the rubbing test.
  • a method of quantifying the content of the functionalizing agent can be appropriately selected in accordance with the type of the functionalizing agent being used.
  • the ratio of the content (Ci) of the functionalizing agent in the functionalized base material after the washing test or the rubbing test relative to the content (Co) of the functionalizing agent in the control functionalized base material, that is, (Ci/Co) * 100 (mass%), is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more.
  • An apparatus for manufacturing a functionalized base material of the present embodiment includes a high-pressure vessel used for mixing a supercritical fluid and a functionalizing agent, and a pulse valve used for discharging, in a gas phase state and/or a supercritical state, the supercritical fluid that is supplied from the high-pressure vessel and in which the functionalizing agent is dissolved, and further includes other components, if desired.
  • a high-pressure vessel used for mixing a supercritical fluid and a functionalizing agent
  • a pulse valve used for discharging, in a gas phase state and/or a supercritical state, the supercritical fluid that is supplied from the high-pressure vessel and in which the functionalizing agent is dissolved, and further includes other components, if desired.
  • a functionalized base material manufacturing apparatus 1 according to the present embodiment will be described with reference to FIG. 1.
  • FIG. 1 is a schematic diagram illustrating a functionalized base material manufacturing apparatus according to the present embodiment.
  • the functionalized base material manufacturing apparatus 1 includes a generation unit 30 that generates a supercritical fluid, a supply unit 40 that supplies a functionalizing agent, a high-pressure vessel 6 used for mixing the supercritical fluid generated in the generation unit 30 with the functionalizing agent supplied from the supply unit 40 to obtain a mixture 20 of the two substances, a pulse valve 10 that discharges the mixture 20 supplied from the high-pressure vessel 6 onto a base material 12, and a pipe 51 that connects the high-pressure vessel 6 and the pulse valve 10.
  • the mixture 20 of the supercritical fluid and the functionalizing agent may be simply referred to as “mixture”.
  • the generation unit 30 includes a gas cylinder 3 storing liquid carbon dioxide, a cooler 31 used for cooling the liquid carbon dioxide supplied from the gas cylinder 3 via a high-pressure valve 101 to a temperature below the saturation temperature, a high- pressure pump 32 that pressurizes the liquid carbon dioxide to a predetermined pressure, a heater 33 used for heating the liquid carbon dioxide supplied from the high-pressure pump 32 to a predetermined temperature, and a back pressure valve 102 that returns excess liquid carbon dioxide from the liquid carbon dioxide supplied from the high-pressure pump 32 to the downstream side of the high-pressure pump 32.
  • An example of the cooler 31 includes a chiller device that causes cooling water to circulate to cool an object to be cooled.
  • an example of the high-pressure pump 32 includes a double plunger pump by which it is possible to control the discharge amount of liquid and prevent pulsation.
  • the cooler 31 and the high-pressure pump 32 are not limited to the examples mentioned above.
  • Liquid carbon dioxide that is pressurized by the high-pressure pump 32 is heated by the heater 33 to vaporize the carbon dioxide.
  • the vaporized carbon dioxide is introduced into the high- pressure vessel 6 and heated and pressurized to bring the carbon dioxide into a supercritical state.
  • the supply unit 40 includes a container 4 storing a functionalizing agent and, if desired, an entrainer, a high-pressure pump 41 that pressurizes the functionalizing agent supplied from the container 4 via a high-pressure valve 106 to a predetermined pressure, and a heater 42 used for heating the functionalizing agent supplied from the high-pressure pump 41 to a predetermined temperature.
  • the high-pressure vessel 6 mixes, under conditions including high pressure, the supercritical fluid supplied from the generation unit 30 via a high-pressure valve 103 and the functionalizing agent supplied from the supply unit 40 via a high-pressure valve 107.
  • An example of the high-pressure vessel 6 is an autoclave. However, the high-pressure vessel 6 is not limited thereto.
  • the high-pressure vessel 6 includes a vessel main body 21 containing a supercritical fluid and a functionalizing agent, a stirring mechanism 22 that stirs the supercritical fluid and the functionalizing agent introduced into the vessel main body 21, a motor 7 that drives the stirring mechanism 22, and a torque meter 23 that measures the rotational force of the stirring mechanism 22.
  • the stirring mechanism 22 examples include a magnetic impeller (an impeller that rotates by the driving force from a motor), a single-shaft screw, a twin-shaft screw with an intermeshing structure, a twin- shaft mixer having a large number of intermeshing or overlapping stirring elements, a kneader having intermeshing helical stirring elements, and a static mixer.
  • the high-pressure vessel 6 preferably further includes a heater 8 used for heating a vessel.
  • the supercritical fluid and the functionalizing agent are not sufficiently mixed. Therefore, the viscosity of the mixture may be high and the torque of the stirring mechanism 22 may be high. However, as the mixing of the supercritical fluid and the functionalizing agent progresses, the viscosity of the mixture decreases. Accordingly, the torque of the stirring mechanism 22 also decreases. Further, when the supercritical fluid and the functionalizing agent are sufficiently mixed with each other, the viscosity of the mixture further decreases. Afterwards, the viscosity stops decreasing. Accordingly, the torque of the stirring mechanism 22 becomes constant. That is, when the torque meter 23 detects that the torque of the stirring mechanism 22 is constant, it can be determined that the supercritical fluid and the functionalizing agent are sufficiently mixed.
  • the supercritical carbon dioxide fluid and the functionalizing agent are mixed under high pressure, for example, under a pressure of about 40 MPa to 50 MPa.
  • a state in which the supercritical carbon dioxide fluid and the functionalizing agent are mixed preferably refers to a state in which the supercritical carbon dioxide fluid and the functionalizing agent are dissolved. Therefore, it is generally not possible to visually check the progress of mixing of the supercritical carbon dioxide fluid and the functionalizing agent by, for example, opening the lid of the high-pressure vessel 6.
  • the torque meter 23 is used to measure the change of the torque in the stirring mechanism 22, it is possible to determine whether the supercritical carbon dioxide fluid and the functionalizing agent are uniformly mixed without visually inspecting the inside of the high-pressure vessel 6. As a result, it is possible to prevent unmixed functionalizing agent from being supplied to the pulse valve 10, and discharge defects of the pulse valve 10 can be prevented.
  • the torque meter 23 may output a torque measurement signal of the stirring mechanism 22 to a control device 24. Further, the control device 24 may determine whether the supercritical fluid and the functionalizing agent are uniformly mixed, based on a torque measurement signal from the torque meter 23. Moreover, the control device 24 may control an opening and closing process of a high-pressure valve 104 arranged downstream of the high-pressure vessel 6, based on the determination result.
  • the high-pressure valve 104 and a high-pressure valve 105 are provided downstream of the high-pressure vessel 6 in the flow path.
  • the high-pressure valve 104 is provided above the high-pressure vessel 6.
  • the high-pressure valve 105 is provided below the high-pressure vessel 6, and a liquid phase portion can be extracted from the high-pressure valve 105, or a waste liquid containing the functionalizing agent can be transferred to a waste liquid tank 9 via a pipe 52.
  • the high-pressure valve 104 opens, the mixture in the high-pressure vessel 6 passes through the pipe 51 and is supplied to the pulse valve 10. It is preferable to provide a heating mechanism or a heat insulating member around the pipe 51.
  • the pipe 51 can be maintained at a predetermined temperature.
  • the supercritical state of the carbon dioxide flowing through the pipe 51 can be maintained, while the supercritical fluid in which the functionalizing agent is dissolved can be conveyed and discharged in a gas phase state and/or a supercritical state.
  • the pulse valve 10 is connected to a front end of the pipe 51. Thus, the pulse valve 10 and the pipe 51 communicate with each other, and the mixture flowing through the pipe 51 is introduced into the pulse valve 10.
  • the pulse valve 10 discharges the introduced mixture in a gas phase state and/or a supercritical state to the base material 12.
  • the base material 12 is placed on a conveyance mechanism 14, and the position of the base material 12 relative to the pulse valve 10 can be controlled by the conveyance mechanism 14, such as a stage.
  • the conveyance mechanism 14 may further include or separately include a heating mechanism 15.
  • the heating mechanism 15 heats the base material 12 to a predetermined temperature. Examples of the heating mechanism 15 include a heater, a hot air generation device, and a laser for localized heating. According to such a configuration, the amount of the functionalizing agent to be applied to each application region of the base material 12 can be controlled by adjusting the discharge amount and the conveyance speed. Thus, it is possible to apply the functionalizing agent to specific regions of the base material, and to implement differentiated dyeing and image formation.
  • a mixture having a temperature of more than 150°C (for example, a temperature of 170°C) and a pressure of about 40 MPa to 50 MPa is introduced into the pulse valve 10.
  • the pulse valve 10 discharges the mixture in a gas phase state and/or a supercritical state toward the base material 12, while maintaining the temperature and the pressure of the mixture at the time of introduction of the mixture.
  • the pulse valve 10 performs high-speed opening and closing operations, so that the opening time is 100 psec or less, for example.
  • the pulse valve 10 can stably discharge a desired amount of the mixture. Note that the pulse valve 10 will be described in detail in the section ⁇ Configuration of Pulse Valve> below.
  • liquid carbon dioxide stored in the gas cylinder 3 passes through the high-pressure valve 101 and is cooled to a temperature equal to or lower than the saturation temperature in a cooler 31.
  • the supercritical carbon dioxide fluid passing through the cooler 31 is introduced into a suction portion of the high-pressure pump 32.
  • the liquid carbon dioxide introduced into the high-pressure pump 32 from the suction portion is pressurized in the high- pressure pump 32 to a predetermined pressure (such as 7.3 MPa, which is the critical pressure of carbon dioxide) or higher.
  • a predetermined pressure such as 7.3 MPa, which is the critical pressure of carbon dioxide
  • the liquid carbon dioxide introduced into the high-pressure pump 32 is returned to the suction portion of the high- pressure pump 32 by the back pressure valve 102.
  • the heater 33 heats the pressurized liquid carbon dioxide to a predetermined temperature (such as 31 °C, which is the critical temperature of carbon dioxide) or higher.
  • a predetermined temperature such as 31 °C, which is the critical temperature of carbon dioxide
  • the generated supercritical carbon dioxide fluid is introduced via the high-pressure valve 103 into the high-pressure vessel 6 which is heated to a predetermined temperature by the heater 8.
  • the stirring mechanism 22 connected to the motor 7 melts and mixes the supercritical carbon dioxide fluid and a functionalizing agent introduced into the high- pressure vessel 6 via a separate path.
  • the heater 8 heats the mixture to about 170°C, for example.
  • the mixture is pressurized to, for example, about 40 MPa to 50 MPa by a predetermined pressure increasing mechanism.
  • the mixture of the supercritical carbon dioxide and the functionalizing agent is obtained by these mixing processes. It is possible to determine whether a uniform mixture is obtained, based on the measurement value of the torque meter 23 measuring the torque of the stirring mechanism 22.
  • the high-pressure valve 104 is opened.
  • the mixture in the high-pressure vessel 6 passes through the pipe 51 and flows toward the pulse valve 10.
  • the pulse valve 10 maintains the temperature and the pressure of the mixture introduced into the pulse valve 10, while repeatedly opening and closing the valves provided within the pulse valve 10 to discharge a desired amount of the mixture onto the base material 12.
  • FIGs. 2 and 3 are vertical cross-sectional views of the pulse valve 10.
  • the pulse valve 10 includes a housing unit 110 having a flow path 112 therein for a fluid to be discharged, a nozzle unit 120 attached to a front end side of the housing unit 110 and discharging the fluid to be discharged, a needle 130 that is inserted into the housing unit 110 and opens and closes the flow path 112 of the housing unit 110, a drive mechanism 140 that reciprocates the needle 130, and a heat insulating flange 150 provided between the housing unit 110 and the drive mechanism 140.
  • the fluid to be discharged in the present embodiment is a mixture of a supercritical fluid and a functionalizing agent.
  • an X direction in the drawings corresponds to a front-rear direction of the pulse valve 10.
  • a Y direction corresponds to a width direction of the pulse valve 10.
  • a Z direction corresponds to a height direction of the pulse valve 10.
  • the housing unit 110 is located at a frontmost portion of the pulse valve 10 and is formed by a case accommodating a mixture introduced from a pipe 441.
  • a front end surface (a frontmost surface on a + side in the X direction) of the housing unit 110 faces the base material 12.
  • the housing unit 110 includes a base portion 111.
  • the flow path 112 for the mixture to be discharged is formed inside the base portion 111.
  • the flow path 112 is formed along the X direction.
  • a first hole portion 113 is formed as a recess in an upper surface (an uppermost surface at the + side of the Z direction) of the base portion 111 so as to be recessed toward the flow path 112.
  • the 1/8 inch pipe 441 attached to the front end of the pipe 51 is inserted into the first hole portion 113.
  • the 1/8 inch pipe 441 inserted into the first hole portion 113 communicates with the flow path 112.
  • the pipe 51 and the 1/8 inch pipe 441 may be collectively referred to as “pipe 51”.
  • the pipe communicating with the flow path 112 may be a pipe having a size or shape different from the 1/8 inch pipe.
  • the first hole portion 113 includes a tapered portion 113T having a diameter that decreases towards the - side in the Z direction, which is the side of the flow path 112. Further, it is preferable that the 1/8 inch pipe 441 is fitted into the first hole portion 113 via a connection ferrule that is deformed by pressure when contacting the tapered portion 113T of the first hole portion 113. A mixture having a high temperature and high pressure flows through the 1/8 inch pipe 441. Therefore, by fitting the 1/8 inch pipe 441 into the first hole portion 113 via the connection ferrule, the 1/8 inch pipe 441 does not detach from the first hole portion 113, even when a mixture having a high temperature and high pressure flows through the 1/8 inch pipe 441.
  • a region of the base portion 111 where the first hole portion 113 is provided may be heated by a heating mechanism (for example, a heating block).
  • a heating mechanism for example, a heating block.
  • the housing unit 100 includes a block 114 on the front end side (the + side in the X direction) from the base portion 111.
  • the block 114 is attached to the base portion 111 via screws 115a and 115b.
  • a second hole portion 116 is formed as a recess in a front end surface of the block 114 (that is, a front end surface of the housing unit 110) and is recessed toward the - side in the X direction, which is the side of the flow path 112.
  • the second hole portion 116 of the present embodiment is formed along the X direction.
  • the nozzle unit 120 is inserted into the second hole portion 116.
  • the second hole portion 116 is an example of a “hole portion”.
  • the pressure of the mixture accommodated in the housing unit 110 is preferably 60 MPa or less.
  • the temperature of the mixture accommodated in the housing unit 110 is preferably 250°C or less. However, the pressure and the temperature of the mixture are not limited thereto.
  • the nozzle unit 120 includes a nozzle base portion 121 that extends along the X direction when the nozzle unit 120 is inserted into the second hole portion 116.
  • a pressure-type connection screw is formed on an outer peripheral portion of the nozzle base portion 121.
  • a thread groove of the connection screw in the nozzle base portion 121 engages with a thread groove formed in the second hole portion 116, so that the nozzle unit 120 is fitted into the second hole portion 116 while being pressed.
  • a nozzle pipe portion 122 having a tube shape along the X direction is formed inside the nozzle base portion 121.
  • the nozzle pipe portion 122 includes a first pipe portion 122a communicating with the front end of the flow path 112, and a second pipe portion 122b that is concentric with the first pipe portion 122a and is provided outside the first pipe portion 122a.
  • the front end of the second pipe portion 122b corresponds to a nozzle hole 123 through which the mixture is discharged onto the base material 12.
  • the nozzle pipe portion 122 has a double pipe structure including the first pipe portion 122a and the second pipe portion 122b. By using such a double pipe structure, the strength of the nozzle pipe portion 122 can be increased. Further, the discharge stability of the mixture supplied from the flow path 112 can be improved.
  • the diameter of the nozzle hole 123 is preferably 5 pm or more and 500 pm or less.
  • the diameter of the nozzle hole 123 is more preferably 100 pm or more and 300 pm or less, and even more preferably 150 pm or more and 250 pm or less.
  • the diameter of the nozzle hole 123 preferably is not less than 5 pm, because in this case, the diameter is too small and the mixture may not be stably discharged.
  • the diameter of the nozzle hole 123 preferably does not exceed 500 pm, because in this case, the thickness of a region of the nozzle unit 120 excluding the nozzle hole 123 is thin, and the nozzle hole 123 may not withstand the pressure when the mixture is discharged.
  • the nozzle unit 120 also includes a connection ferrule 124 provided on an outer peripheral portion of the nozzle pipe portion 122.
  • the connection ferrule 124 is a member made of stainless steel, which substantially has a truncated cone shape of which a diameter decreases toward the - side in the X direction.
  • connection ferrule 124 collides with a tapered portion 116 T of the second hole portion 116. After colliding with the tapered portion 116T, the connection ferrule 124 moves further into the second hole portion 116 and is inserted into the inside of the tapered portion 116T. As a result, the connection ferrule 124 is pressed and deformed by being pressed against the tapered portion 116T of the second hole portion 116. This restricts further movement of the connection ferrule 124. As a result, the nozzle unit 120 is fitted into the second hole portion 116 and firmly fixed to the block 114.
  • the nozzle unit 120 is fixed to the block 114 of the housing unit 110 via the connection ferrule 124, and thus, it is possible to improve the pressure resistance and the durability. In particular, a mixture having high pressure flows through the nozzle unit 120, and thus, it is preferable to join the nozzle unit 120 and the housing unit 110 via the connection ferrule 124. [0095] ⁇ Needle>>
  • the needle 130 is inserted into the housing unit 110 and functions as a valve that opens and closes the flow path 112 of the housing unit 110.
  • a front end of the needle 130 closes an extremely small hole 132 of an orifice 131 provided between the flow path 112 and a rear end of the nozzle pipe portion 122 of the nozzle unit 120.
  • the flow path 112 is closed.
  • the needle 130 retracts, and the front end of the needle 130 moves away from the orifice 131. Therefore, the extremely small hole 132 of the orifice 131 is opened, and the flow path 112 opens.
  • the response speed of the needle 130 is preferably 100 psec or less.
  • the drive mechanism 140 is a mechanical unit that is connected to the needle 130 and reciprocates the needle 130.
  • the drive mechanism 140 includes an extension bar 141 having an elongated tubular shape that is connected to a rear end of the needle 130, and a piezoelectric actuator 142 that reciprocates the extension bar 141 at a predetermined speed.
  • the extension bar 141 is preferably made of a material having a low coefficient of thermal expansion to avoid thermal expansion due to heat transfer from the needle contacting the mixture.
  • materials having a low coefficient of thermal expansion include, but are not limited to, INVAR, which is an alloy of iron and nickel, and SUPER INVAR, which is an alloy of iron, nickel, and cobalt.
  • SUPER INVAR which has an extremely low coefficient of thermal expansion, is preferable.
  • a mixture having a temperature of about 250°C flows through the flow path 112.
  • a front end region of the needle 130 is inserted into the flow path 112 and contacts the mixture.
  • the extension bar 141 is continuously provided with the needle 130. Therefore, heat is transferred from the mixture to the extension bar 141 via the needle 130.
  • the extension bar 141 strongly expands by thermal expansion, the range of the reciprocating movement of the extension bar 141 changes, and the range of the reciprocating movement of the needle 130 also changes. As a result, it may not be possible to accurately supply a desired amount of the mixture contained in the flow path 112 toward the nozzle unit 120.
  • extension bar 141 is made of a material having a low coefficient of thermal expansion, such as SUPER INVAR, thermal expansion of the extension bar 141 can be suppressed, even if heat from the mixture is transferred from the needle 130. As a result, a desired amount of the mixture can be accurately supplied toward the nozzle unit 120.
  • extension bar 141 from a material that suppresses thermal expansion, such as SUPER INVAR, the operational stability of the piezoelectric actuator 142 can be ensured.
  • the piezoelectric actuator 142 includes a piezoelectric element that deforms by expanding and contracting in response to the application of a pulse- shaped voltage signal.
  • the piezoelectric actuator 142 deforms by expanding and contracting in the X direction.
  • the piezoelectric actuator 142 is preferably a ring actuator provided around the outer periphery of the extension bar 141.
  • the piezoelectric actuator 142 can be formed from a thin piezoelectric element layer, and thus, a large amount of displacement can be obtained at a low voltage. [0103] In the present embodiment, the piezoelectric actuator 142 is used as the actuator of the drive mechanism 140, but other types of actuators may also be used. However, the piezoelectric actuator 142 is preferably used to achieve a high-speed response in which the valves are opened and closed in less than about 100 psec.
  • the heat insulating flange 150 prevents heat transfer from the housing unit 110 toward the piezoelectric actuator 142.
  • the material of the heat insulating flange 150 is not particularly limited, but is preferably made of a ceramic having high heat insulating properties.
  • FIG. 4 is a vertical cross-sectional view of the pulse valve 10a according to the second embodiment.
  • FIG. 5 is a cross-sectional view of the pulse valve 10a taken along line A-A indicated in FIG. 4.
  • the flow path 112 includes a plurality of divided paths 112a to 112d each extending along the X direction.
  • the positions of the divided paths 112a to 112d are not particularly limited, but are preferably in a front end region in the vicinity of the orifice 131 in the flow path 112.
  • the divided paths 112a to 112d are arranged along the circumferential direction of the needle 130 and are formed by gaps extending outward in a radial direction from an outer peripheral wall 135 of the needle 130. Further, boundary walls of adjacent divided paths, such as a boundary wall between the divided path 112a and the divided path 112b, a boundary wall between the divided path 112b and the divided path 112c, a boundary wall between the divided path 112c and the divided path 112d, and a boundary wall between the divided path 112d and the divided path 112a, contact the outer peripheral wall 135 of the needle 130.
  • the needle 130 can be guided so as to be positioned at the center of the flow path 112, even after the needle 130 reciprocates. As a result, a desired amount of the mixture can be accurately supplied toward the nozzle unit 120.
  • a PET knit (manufactured by Uni Textile Co., Ltd., fabric weight: 138 g/m 2 , yarn count: 75/72) was used as a fabric-like base material to which a functionalizing agent was to be applied.
  • the dye Disperse Blue 14 was used as the functionalizing agent.
  • the functionalized base material manufacturing apparatus 1 illustrated in FIG. 1 was used to supply 5 mg of Disperse Blue 14 to the high-pressure vessel 6 having a volume of 400 ml at a temperature of 135°C and a pressure of 40 MPa, and the dye was dissolved in a supercritical carbon dioxide fluid.
  • the base material was cut to a size of 8 cm x 10 cm, placed on the stage of the conveyance mechanism 14, and heated to a surface temperature of 150°C by the heating mechanism 15.
  • Example 1 a functionalized base material of Example 1 was prepared.
  • Example 1 The base material used in Example 1, that is, an undyed fabric, was used as the functionalized base material in Comparative Example 1.
  • the obtained base material was reduced and cleaned at 80°C for 20 minutes in an aqueous solution containing 1 g of a concentrated solution of SUNMORL RC-700E (manufactured by Nicca Chemical Co., Ltd.), which is used as a surfactant or soaping agent, 2 g of hydrosulfite, and 2 g of NaOH with respect to 1 L of water, to prepare a functionalized base material of Comparative Example 3.
  • SUNMORL RC-700E manufactured by Nicca Chemical Co., Ltd.
  • Each functionalized base material was cut into a size of 1 cm x 1 cm to be used as an evaluation sample.
  • Each evaluation sample was divided into four equal pieces. One piece was placed in a 10 ml vial, and about 5 ml of tetrahydrofuran (THF) was added. The mixture was treated with ultrasonic waves at 40 KHz for 30 minutes at an initial temperature of 25°C, and then allowed to stand one night to obtain a THF extract. About 9.5 ml of acetonitrile was added to 1 ml of the THF extract to obtain a sample for analyzing the surface oligomers.
  • the oligomers extracted by the above-described extraction with tetrahydrofuran were defined as oligomers present on the surface of the functionalized base material, and were subsequently subjected to HPLC analysis.
  • the sample for analyzing the surface oligomers was analyzed by HPLC under the following HPLC conditions.
  • Phase A 10 mM aqueous solution of ammonium formate
  • Phase B acetonitrile
  • a calibration curve for dimethyl phthalate was calculated from the measurement results of a standard solution of DMP.
  • DMP standard solution having a known concentration of 1200 ppm, which was then progressively diluted and used.
  • the content in terms of DMP was calculated from the peak area in HPLC corresponding to the oligomers.
  • the content in terms of DMP was converted into the content of CDMP, assuming that the molar absorption coefficient of CDMP is three times the molar absorption coefficient of DMP.
  • the content of oligomers on the surface of each of the obtained functionalized base materials is indicated in Table 1.
  • Each evaluation sample was divided into four equal pieces, one of which was placed in a 10 ml vial, and about 0.6 ml of hexafluoropropanol was added to the vial.
  • the vial was left standing for about 2 hours, and then, about 9.4 ml of acetonitrile was added.
  • the obtained mixture was filtered through a PTFE filter having a pore size of 0.2 pm to obtain a sample for HPLC analysis.
  • Comparative Example 3 water dyeing
  • Comparative Example 3 water dyeing
  • Comparative Example 3 water dyeing
  • Comparative Example 3 water dyeing
  • the dye liquor was removed in a state where the oligomers were dissolved in the dye liquor, so that the oligomers were less likely to be refixed to the surface of the functionalized base material.
  • the increase (re-fixation) of surface oligomers was suppressed, and at the same time, it is considered that the content of internal oligomers was also reduced.
  • the oligomers migrate due to heating.
  • the carbon dioxide density is low when the carbon dioxide fluid is applied to the base material. Therefore, the amount of oligomers moving to the surface of the functionalized base material (content of surface oligomers) is small.
  • Example 1 the base material was not treated with a surfactant, and thus, no surfactant would be detected. This confirmed that, when a surfactant is used, the surfactant can be distinguished from the components adhering to the fabric.
  • Phase A 10 mM aqueous solution of ammonium formate
  • Phase B acetonitrile
  • phase A/phase B volume ratio
  • phase A/phase B volume ratio
  • phase A/phase B volume ratio
  • a functionalized base material obtained by a dyeing method using water can be clearly distinguished from the functionalized base material of the present embodiment by examining the content of surfactants by LC-MS analysis or the like, to confirm that the functionalized base material of the present embodiment is substantially free of surfactants.
  • the functionalizing agent (dye) in Example 1 was changed from Disperse Blue 14 to Disperse Orange 25, and the application step was implemented under the following conditions.
  • the functionalized base material manufacturing apparatus 1 illustrated in FIG. 1 was used to supply 5 mg of Disperse Orange 25 and 15 g of acetonitrile as an entrainer to the high- pressure vessel 6 having a volume of 400 ml at a temperature of 175°C and a pressure of 25 MPa, and Disperse Orange 25 and acetonitrile were dissolved in a supercritical carbon dioxide fluid.
  • the base material was cut to a size of 8 cm x 10 cm, placed on the stage of the conveyance mechanism 14, and heated to a surface temperature of 150°C by the heating mechanism 15.
  • Example 2 The functionalized base material obtained in Example 2 was subjected to a washing fastness test based on JIS L 0844 No. A-2. The results indicated grades of 4 and 5 for discoloration after washing and grade 4 for staining after washing. Further, a rubbing fastness test was conducted using a dry test based on the rubbing tester type II method of JIS L 0849. The results were equivalent to grades 3 and 4 for staining after rubbing. These tests were outsourced to the Kaken Test Center, which is a general incorporated foundation.
  • aspects of the present disclosure include, for example, the following.
  • a method of manufacturing a functionalized base material includes: discharging and applying to a base material a supercritical fluid in a gas phase state or a supercritical state in which a functionalizing agent is dissolved.
  • the base material comprises a polymeric molded body.
  • the functionalizing agent comprises a dye.
  • the base material is in a form of fabric.
  • the functionalizing agent comprises at least one selected from the group consisting of a preservative, an antifungal agent, a waterproofing agent, and a conductive agent.
  • the functionalizing agent includes a first functionalizing agent and a second functionalizing agent
  • the discharging and applying includes: discharging and applying to the base material a supercritical fluid in a gas phase state in which the first functionalizing agent is dissolved, and discharging and applying to the base material a supercritical fluid in a gas phase state in which the second functionalizing agent is dissolved.
  • a functionalized base material includes: a base material including oligomers where a content of internal oligomers is 50 mass% or more of all the oligomers in the base material; and a functionalizing agent, and the functionalized base material is substantially free of a surfactant.
  • the base material comprises a polymeric molded body.
  • the content of internal oligomers is 0.8 mass% or more of the functionalized base material.
  • the functionalizing agent is in a form of fabric.
  • the functionalizing agent comprises a dye.
  • a discoloration degree and a staining degree, evaluated by a washing fastness test according to JIS L 0844 No. A-2 are grade 4 or higher and grade3 or higher, respectively, and a staining degree, evaluated by a rubbing fastness test that is a dry test based according to a rubbing tester type II method of JIS L 0849, is grade 3 to 4 or higher.
  • the functionalizing agent comprises at least one selected from the group consisting of a preservative, an antifungal agent, a waterproofing agent, and a conductive agent.
  • a content of the functionalizing agent in a first region of the functionalized base material is different from a content of the functionalizing agent in a second region of the functionalized base material.
  • the functionalizing agent includes a first functionalizing agent and a second functionalizing agent.
  • an apparatus for manufacturing a functionalized base material includes a high-pressure vessel to mix and dissolve a functionalizing agent in a supercritical fluid, and a pulse valve to discharge the supercritical fluid in a gas phase state or a supercritical state in which the functionalizing agent is dissolved, supplied from the high-pressure vessel.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Coloring (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatment Of Fiber Materials (AREA)

Abstract

A method of manufacturing a functionalized base material is provided. The method includes discharging and applying to a base material a supercritical fluid in a gas phase state or a supercritical state in which the functionalizing agent is dissolved.

Description

[DESCRIPTION]
[Title of Invention]
METHOD OF MANUFACTURING FUNCTIONALIZED BASE MATERIAL, FUNCTIONALIZED BASE MATERIAL, AND APPARATUS FOR MANUFACTURING FUNCTIONALIZED BASE MATERIAL [Technical Field] [0001]
The present disclosure relates to a method of manufacturing a functionalized base material, a functionalized base material, and an apparatus for manufacturing a functionalized base material.
[Background Art]
[0002]
In conventional water-based dyeing of fabrics, chemicals such as solvents and surfactants are used. Therefore, a large amount of waste liquid to be treated is produced, and a large amount of energy is required for drying, so that the environmental impact is extremely high. In response to this issue, dyeing using supercritical carbon dioxide is being investigated.
[0003]
A method for treating a molded resin body has been reported as a batch-type waterless dyeing method. In the method, a supercritical fluid in which a colorant or a functional agent, or both a colorant and a functional agent, are dissolved is contacted with the molded resin body containing an additive. Thus, the additive is extracted from the molded resin body, and the colorant or the functional agent, or both the colorant and the functional agent, are applied to a surface layer of the molded resin body (see, for example, PTL 1).
[0004]
Further, a method for imparting a function to a polymeric molded product has been reported as a continuous waterless dyeing method. In the method, a supercritical fluid is sprayed onto a polymeric molded product and a functionalizing agent is fixed to the polymeric molded product (see, for example, PTL 2).
[Citation List]
[Patent Literature]
[PTL 1]
Japanese Unexamined Patent Application Publication No. 2007-091805
[PTL 2]
WO 2008/069041
[Summary of Invention]
[Technical Problem]
[0005]
An object of the present disclosure is to provide a method of manufacturing a functionalized base material in which no chemicals such as surfactants or large amounts of water are used, and by which surface contamination of fibers due to elution of oligomers and deposition of the eluted oligomers inside an apparatus can be reduced. In the method, a functionalizing agent can be adsorbed inside a base material or uniformly attached to the surface of the base material and diffused into the base material. The method can use a continuous process and control the amount of the functionalizing agent applied to each discharge site, so that differentiated dyeing and image formation can be implemented with a plurality of types of functionalizing agents.
[Solution to Problem]
[0006]
[Advantageous Effects of Invention]
Embodiments of the present disclosure provide a method of manufacturing a functionalized base material. The method includes discharging and applying to a base material a supercritical fluid in a gas phase state or a supercritical state in which the functionalizing agent is dissolved.
[0007]
According to one embodiment of the present disclosure, a method of manufacturing a functionalized base material can be provided in which no chemicals such as surfactants or large amounts of water are used, and by which surface contamination of fibers due to elution of oligomers and deposition of the eluted oligomers inside an apparatus can be reduced. In the method, a functionalizing agent can be adsorbed inside a base material or uniformly attached to the surface of the base material and diffused into the base material. The method can use a continuous process and control the amount of the functionalizing agent applied to each application site, so that differentiated dyeing and image formation can be implemented with a plurality of types of functionalizing agents.
[Brief Description of Drawings]
[0008]
A more complete appreciation of embodiments of the present disclosure and many of the attendant advantages and features thereof can be readily obtained and understood from the following detailed description with reference to the accompanying drawings.
FIG. 1 is a schematic diagram illustrating an apparatus for manufacturing a functionalized base material.
FIG. 2 is a cross-sectional view of a pulse valve in an apparatus for manufacturing a functionalized base material.
FIG. 3 is a partial cross-sectional view of the pulse valve illustrated in FIG. 2.
FIG. 4 is a cross-sectional view of a pulse valve in an apparatus for manufacturing a functionalized base material.
FIG. 5 is a cross-sectional view of the pulse valve taken along line A-A in FIG. 4. FIG. 6 is a spectrum derived from a surfactant in a functionalized base material of Comparative Example 3.
FIG. 7 is a spectrum of a surfactant. The accompanying drawings are intended to depict embodiments of the present disclosure and should not be interpreted to limit the scope thereof. The accompanying drawings are not to be considered as drawn to scale unless explicitly noted. Also, identical or similar reference numerals designate identical or similar components throughout the several views. [Description of Embodiments]
In describing embodiments illustrated in the drawings, specific terminology is employed for the sake of clarity. However, the disclosure of this specification is not intended to be limited to the specific terminology so selected and it is to be understood that each specific element includes all technical equivalents that have a similar function, operate in a similar manner, and achieve a similar result.
Referring now to the drawings, embodiments of the present disclosure are described below. As used herein, the singular forms “a”, “an”, and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
[0009]
(Method of Manufacturing Functionalized Base Material)
A method of manufacturing a functionalized base material of the present embodiment is a method of manufacturing a functionalized base material having a base material and a functionalizing agent, and includes a step of discharging and applying to the base material a supercritical fluid in a gas phase state or a supercritical state in which the functionalizing agent is dissolved (i.e., application step), and further includes other steps, if desired.
The method of manufacturing a functionalized base material can be suitably implemented by an apparatus for manufacturing a functionalized base material of the present embodiment, which will be described later.
[0010]
The present disclosure responds to the following issues found by the inventors of the present invention.
That is, in a conventional batch-type waterless dyeing method, oligomers contained in fibers are eluted onto the surface of the fibers and accumulate in the batch, and in addition, the eluted oligomers reattach to the fibers, so that uniform dyeing properties deteriorate. The size of the fibers or fabric is limited to a size that can be stored in a batch container, the fabric has to be cut for each batch, and all of the fibers or fabric have to be dyed for each batch.
Further, in the continuous waterless dyeing method described in PTE 2, a reactor including a gap having substantially an inverted T-shape in its cross-sectional view is used, and a functional material liquid and supercritical carbon dioxide are mixed in a mixing coil and sprayed onto a polymeric molded product such as a fiber that is moved through the gap. A part of the functional material that does not completely dissolve in the supercritical carbon dioxide is sprayed as a liquid, and thus, it is difficult to apply the functional material uniformly or locally onto the fiber, and it is difficult to control the amount of the functional material to be applied.
[0011] As a result of diligent research by the inventors of the present invention to achieve the abovedescribed object, the inventors of the present invention have found the following. That is, by providing a step of discharging and applying to the base material a supercritical fluid that contains the functionalizing agent and is in a gas phase state and/or a supercritical state, it is possible to reduce contamination of the surface of the fibers due to the elution of oligomers and deposition of eluted oligomers within the apparatus, without using chemicals such as surfactants or a large amount of water. Further, it is possible to adsorb the functionalizing agent inside the base material or to cause the functionalizing agent to uniformly adhere to the surface of the base material to diffuse the functionalizing agent inside the base material. It is possible to use a continuous process and control the amount of the functionalizing agent applied to each application site, so that differentiated dyeing and image formation can be implemented with a plurality of types of functionalizing agents. These findings led to the completion of the present disclosure.
[0012]
Application Step>
The application step is a step of discharging and applying to the base material a supercritical fluid that contains the functionalizing agent and is in a gas phase state or a supercritical state. The application step can be suitably implemented by using a high-pressure vessel and a pulse valve in an apparatus for manufacturing a functionalized base material of the present embodiment, which will be described later.
The discharged supercritical fluid does not include a liquid phase. [0013]
To discharge and apply to the base material the supercritical fluid that contains the functionalizing agent and is in a gas phase state or a supercritical state, the temperature and the pressure of a high-pressure vessel are controlled and the supercritical fluid is sprayed onto a polymer structure body from a nozzle unit so that the supercritical fluid or a mixture of the supercritical fluid and an entrainer does not transition from the supercritical state to a liquid state or a solid state when the supercritical fluid containing the functionalizing agent is discharged from the nozzle unit (that is, when the fluid expands). For example, when the supercritical fluid is a supercritical carbon dioxide fluid and does not contain an entrainer, referring to the Mollier diagram for carbon dioxide alone, the supercritical fluid can be discharged and applied in a gas phase state or a supercritical state by controlling the high- pressure vessel to achieve a temperature of 390 K (about 117 degrees) or higher at 25 MPa, and 408 K (about 135 degrees) or higher at 40 MPa.
[0014]
In the application step, the base material to which the functionalizing agent is to be applied is conveyed or a discharge position of a pulse valve or the like with respect to the base material is scanned. Therefore, the functionalizing agent can be discharged in a continuous process. In addition, the amount of the functionalizing agent to be applied to each application region of the base material can be controlled, and thus, it is possible to apply the functionalizing agent to specific regions of the base material, and to implement differentiated dyeing and image formation. Specific examples of these aspects include an aspect in which the content of the functionalizing agent in a first region of the functionalized base material is different from the content of the functionalizing agent in a second region of the functionalized base material. [0015]
The application step may include a first application step and a second application step. Specifically, in a preferred aspect of the method of manufacturing a functionalized base material, the functionalizing agent contains a first functionalizing agent and a second functionalizing agent. In this case, in the first application step, a supercritical fluid in which the first functionalizing agent is dissolved is discharged and applied to the base material in a gas phase state and/or a supercritical state. In the second application step, a supercritical fluid in which the second functionalizing agent is dissolved is discharged and applied to the base material in a gas phase state and/or a supercritical state.
The first functionalizing agent and the second functionalizing agent are not particularly limited and can be selected according to a purpose from functionalizing agents that are different from each other.
According to the above-described aspect, it is possible to implement differentiated dyeing and image formation with a plurality of types of functionalizing agents.
[0016]
- Base Material -
The base material is not particularly limited and can be appropriately selected according to a purpose. However, the base material is preferably a polymeric molded body molded of a polymer.
The material of the polymeric molded body is not particularly limited and can be appropriately selected according to a purpose. Examples of the material include, but are not limited to, polyester-based polymers such as polyethylene terephthalate (PET); polyolefin- based polymers; polyamide -based polymers such as Nylon 6; acrylate-based polymers such as polyacrylonitrile; acetate -based polymers; polyvinyl chloride-based polymers; and aramid- based polymers.
The polymeric molded body may be in the form of fibers such as raw yarn and twisted yarn, in the form of fabrics such as woven fabric, knitted fabric, and nonwoven fabric, or in the form of a film or a plate, and any of these shapes may be suitably applied. Among these shapes, the polymeric molded body is preferably a fabric, a film, or a plate, and more preferably a fabric, because in this case, it is possible to advantageously realize the possibility of differentiated dyeing and image formation.
[0017]
As the polyester-based polymer, polyethylene terephthalate is preferred.
The polyethylene terephthalate may contain a copolymerization component, and preferably contains 90 mol% or more of repeating units of polyethylene terephthalate, and more preferably contains 95 mol% or more of repeating units of polyethylene terephthalate. The polymeric molded body may contain any copolymerization component, and may also contain additives such as stabilizers, antioxidants, antistatic agents, fluorescent whitening agents, catalysts, and colorants.
[0018]
- Supercritical Fluid -
The supercritical fluid refers to a fluid under supercritical conditions including a temperature equal to or higher than the critical temperature and a pressure equal to or higher than the critical pressure. For example, supercritical carbon dioxide fluid refers to a carbon dioxide fluid under supercritical conditions including a temperature of 31.1 °C or higher, which is the critical temperature of carbon dioxide, and a pressure of 7.48 MPa or higher, which is the critical pressure of carbon dioxide.
[0019]
The supercritical fluid may also be used together with an entrainer (i.e., auxiliary solvent). Examples of the entrainer include, but are not limited to, alcohols such as methanol, ethanol, and propanol; ketones such as acetone and methyl ethyl ketone; and organic solvents such as toluene, ethyl acetate, and tetrahydrofuran. These entrainers may be used alone or in combination of two or more types.
[0020]
- Functionalizing Agent -
The functionalizing agent is not particularly limited and can be appropriately selected according to a purpose and the physicochemical characteristics of the base material. Examples of the functionalizing agent include, but are not limited to, dyes; preservatives, antifungal agents, waterproofing agents, conductive agents, ultraviolet absorbing agents, strength enhancing agents, oxidizing agents, neutralizing agents, metals, catalyst deactivators, slipping agents, light stabilizers, anti-tack agents, lubricants, fire retardants, coupling agents, processing aids, antistatic agents, nucleating agents, and foaming agents. Among these functionalizing agents, dyes are preferred in dyeing applications, and preservatives, antifungal agents, waterproofing agents, and conductive agents are preferred in various other applications.
These functionalizing agents may be used alone or in combination of two or more types. Specifically, two or more types of functionalizing agents may be mixed and applied in one application step, or two or more types of functionalizing agents may be applied individually in two or more application steps.
[0021]
The functionalizing agent is suitably selected so that the functionalizing agent does not dissolve from the functionalized base material under practical use conditions, and the functionalizing agent substantially does not dissolve or only a very small amount of the functionalizing agent dissolves in the functionalized base material and the base material under normal conditions.
[0022] Examples of the dyes include, but are not limited to, disperse dyes, acid dyes, acid mordant dyes, basic dyes, direct dyes, construction dyes, reactive dyes, and naphthol dyes.
Among these dyes, disperse dyes are preferred, because disperse dyes have excellent solubility in the supercritical carbon dioxide fluid. In an aqueous dyeing process using a disperse dye, a dispersant is used to stably disperse the disperse dye in water. However, in the method of manufacturing a functionalized base material according to the present embodiment, the disperse dye can be mixed with a supercritical fluid and used without using a dispersant. [0023]
Examples of disperse dyes include, but are not limited to, Disperse Yellow 54, Disperse Yellow 122, Disperse Yellow 124, Disperse Yellow 128, Disperse Yellow 134, Disperse Yellow 140, Disperse Orange 5, Disperse Orange 25, Disperse Orange 37, Disperse Orange 93, Disperse Orange 103, Disperse Orange 112, Disperse Orange 134, Disperse Orange 370, Disperse Green 7, Disperse Violet 61, Disperse Violet 63, Disperse Brown 1, Disperse Brown 13, Disperse Blue 14, Disperse Blue 27, Disperse Blue 54, Disperse Blue 56, Disperse Blue 176, Disperse Blue 182, Disperse Blue 193, Disperse Red 60, Disperse Red 146, Disperse Red 199, Disperse Red 202, Disperse Red 204, and Disperse Red 291. These disperse dyes may be used alone or in combination of two or more types.
[0024]
Examples of the preservatives and the antifungal agents include, but are not limited to, MARUKACIDE YP-DP (manufactured by Osaka Kasei Co.), AMOLDEN HS (manufactured by Daiwa Chemical Industries Co., Ltd.), catechin, chitosan, flavone, acrylonitrile, and polyanions of which each molecule has a plurality of anionic functional groups such as carboxyl groups, sulfonic acid groups, sulfate groups, and phosphate groups.
Examples of the waterproofing agents include, but are not limited to, NEOSEED (manufactured by Nicca Chemical Co., Ltd.), QUEENSET PSO-5500 (manufactured by Kotani Chemical Industry Co., Ltd.), and POLONCOAT-E (manufactured by Shin-Etsu Chemical Co., Ltd.).
Examples of the conductive agents include, but are not limited to, silver acetylacetonate, dimethylcyclooctadiene platinum II, and palladium bisacetylacetonate.
Examples of the fire retardants include, but are not limited to, aromatic condensed phosphate esters.
[0025]
Examples of the ultraviolet absorbing agents include, but are not limited to, benzotriazole- based agents and benzophenone -based agents.
Examples of the strength enhancing agents include, but are not limited to, silicone oil. Examples of the neutralizing agents or catalyst deactivators include, but are not limited to, zinc oxide, zinc stearate, aliphatic amines, and aliphatic amides.
Examples of the metals include, but are not limited to, copper, silver, nickel, and gold. Examples of the slipping agents include, but are not limited to, erucamide, oleamide, and ethylene bisstearamide. Examples of the light stabilizers include, but are not limited to, benzophenone -based light stabilizers.
Examples of the anti-tack agents include, but are not limited to, diatomaceous earth, silica, clay, and talc.
Examples of the lubricants include, but are not limited to, organic modified polydimethylsiloxane. Examples of the processing aids include, but are not limited to, calcium stearate and organic modified polydimethylsiloxane.
Examples of the antistatic agents include, but are not limited to, glycerol monostearate, ethoxylated amines, polyethylene glycol esters, and quaternary ammonium compounds. Examples of the foaming agents include, but are not limited to, azodicarbonamide and sodium bicarbonate.
[0026]
(Functionalized Base Material)
The functionalized base material of the present embodiment is a functionalized base material including a base material and a functionalizing agent.
The functionalized base material is substantially free of surfactants, and the content of internal oligomers is 50 mass% or more of all oligomers in the base material.
[0027]
<Base Material >
The base material is not particularly limited and may be appropriately selected according to a purpose from the materials mentioned above in the description of the base material in the method of manufacturing a functionalized base material of the present embodiment.
The shape of the base material and the functionalized base material is not particularly limited and can be appropriately selected according to a purpose. However, the base material and the functionalized base material are preferably in the form of a fabric.
[0028]
<Functionalizing Agent>
The functionalizing agent is not particularly limited and can be appropriately selected according to a purpose from the materials mentioned above in the description of the functionalizing agent in the method of manufacturing a functionalized base material of the present embodiment.
The functionalizing agent is not particularly limited and can be appropriately selected according to a purpose. In one aspect, the functionalizing agent is preferably a dye, and in another aspect or an additional aspect, the functionalizing agent includes preferably one or more types selected from the group consisting of a preservative, an antifungal agent, a waterproofing agent, and a conductive agent.
[0029]
According to the functionalized base material of the present embodiment, it is possible to apply a functionalizing agent to a specific site of a base material, and to realize differentiated dyeing and image formation. Specific examples of these aspects include an aspect in which the content of the functionalizing agent in a first region of the functionalized base material is different from the content of the functionalizing agent in a second region of the functionalized base material.
[0030]
Another preferred aspect is an aspect in which the functionalizing agent includes a plurality of functionalizing agents, for example, an aspect in which the functionalizing agent includes a first functionalizing agent and a second functionalizing agent. In this case, by mixing and applying the first functionalizing agent and the second functionalizing agent, a functionalized base material may be obtained that contains the first functionalizing agent and the second functionalizing agent in specific regions of the functionalized base material. Further, by implementing a first application step and a second application step, a functionalized base material may be obtained in which the content and the application pattern of the first functionalizing agent and the content and the application pattern of the second functionalizing agent are different in each region of the functionalized base material. Any of these aspects can be appropriately selected according to a purpose.
[0031]
< Oligomer >
The content of internal oligomers is 50 mass% or more, preferably 60 mass% or more, and more preferably 70 mass% or more, of all the oligomers in the base material. The content of surface oligomers is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less, of all the oligomers in the base material.
[0032]
As described above, in a conventional batch-type waterless dyeing method, oligomers contained in fibers are eluted onto the surface of the fibers and accumulate in the batch, and in addition, the eluted oligomers reattach to the fibers, so that uniform dyeing properties deteriorate. Thus, compared to an undyed fiber, in the fiber dyed by the batch-type waterless dyeing method, the content of internal oligomers decreases (that is, less than 50% of all the oligomers) and the content of the surface oligomers increases (for example, more than 50% of all the oligomers).
[0033]
On the other hand, according to the method of manufacturing a functionalized base material and the functionalized base material of the present embodiment, the base material is not maintained in a heated state within a batch for a long period of time as in the batch-type waterless dyeing method. A supercritical fluid in which a functionalizing agent is dissolved is discharged and applied to the base material in a gas phase state and/or a supercritical state. Therefore, it is possible to control the applied amount of the supercritical fluid locally and reduce the time the base material is exposed to an atmosphere in which oligomers are easily dissolved. Therefore, according to the present embodiment, the supercritical fluid is applied under reduced pressure, and thus, the treatment time is short. Therefore, oligomers are less likely to be eluted from inside the base material, so that the oligomers do not remain in the batch, the loss of internal oligomers within the functionalized base material is reduced, and the elution of surface oligomers is reduced.
[0034]
In general, reports indicate that polyester fibers before dyeing contain a total amount of oligomers of about 1 mass%, and the amount of surface oligomers adhering to the surface of the polyester fibers is about 0.1 mass% (Development of a Polyester Oligomer Removal Agent: Jun Kamitani, Yasunari Sawanoi, and Hiroyuki Hasebe). As will become apparent from the Examples described later, the total oligomer content was about 1.4 mass%, and the content of surface oligomers was 0.11 mass%, which is similar to the above-mentioned report (see Comparative Example 1 in Table 1). From the above, by confirming the content and the distribution of oligomers (and whether surfactants are present) in the functionalized base material, it is possible to distinguish between a dyed product obtained by conventional batchtype waterless dyeing (and water dyeing) and the functionalized base material of the present embodiment.
[0035]
To reduce the elution of oligomers from the base material, the content of the internal oligomer in the functionalized base material is preferably 0.8 mass% or more, more preferably 0.9 mass% or more, and even more preferably 1.0 mass% or more, of the functionalized base material. The content of the internal oligomers in the functionalized base material can be appropriately selected in accordance with the oligomer content in the base material being used, and is preferably 60 mass% or more, more preferably 70 mass% or more, and even more preferably 80 mass% or more, of all the oligomer in the base material. The content of the surface oligomers in the functionalized base material is preferably 0.7 mass% or less, more preferably 0.6 mass% or less, and even more preferably 0.5 mass% or less, of the functionalized base material.
[0036]
The content of all oligomers in the functionalized base material can be determined by appropriately selecting a known method depending on the type of base material used. For example, the base material can be completely dissolved in a solvent that can dissolve the base material, and then, a polymer can be precipitated using an appropriate solvent. The precipitated polymer can be removed by filtration to extract and quantitatively analyze all oligomers.
Specifically, when the base material is polyethylene terephthalate (PET), the functionalized base material is completely dissolved in hexafluoropropanol, the polymer is precipitated with acetonitrile, and then, the precipitate is filtered through a filter to obtain a hexafluoropropanol extract. The obtained extract is analyzed by high-pressure liquid chromatography (HPLC) analysis and the oligomers are quantified to measure the oligomer content.
[0037]
- Extraction with Hexafluoropropanol - Specifically, a sample for analyzing the content of all oligomers can be obtained by the following procedure. A functionalized base material is cut to obtain a piece having a size of 1 cm x 1 cm, which is used as an evaluation sample. The evaluation sample is divided into four equal pieces, one of which is placed in a 10 ml vial, and about 0.6 ml of hexafluoropropanol is added to the vial. The vial is left standing for about 2 hours, and then, about 9.4 ml of acetonitrile is added. The obtained mixture is filtered through a PTFE filter having a pore size of 0.2 pm to obtain a sample for analyzing the content of all oligomers.
[0038]
The content of surface oligomers in the functionalized base material can be determined by appropriately selecting a known method in accordance with the type of the base material being used. For example, the surface oligomers can be extracted and quantitatively analyzed by dissolving the surface of the base material in a solvent that can dissolve the surface of the base material.
Specifically, when the base material is polyethylene terephthalate (PET), the functionalized base material is subjected to an extraction with tetrahydrofuran, the obtained extract is analyzed by HPLC analysis and the oligomers are quantified. The content of internal oligomers can be calculated by subtracting the content of surface oligomers from the content of all oligomers.
[0039]
- Extraction with Tetrahydrofuran -
Specifically, a sample for analyzing the content of surface oligomers can be obtained by the following procedure. A part (about 0.015 g) of a functionalized base material is separated to be used as an evaluation sample. The evaluation sample is placed in a 10 ml vial, and about 5 ml of THF is added to the vial. The mixture is treated with ultrasonic waves at 40 KHz for 30 minutes at an initial temperature of 25°C, and then allowed to stand one night to obtain a THF extract. About 9.5 ml of acetonitrile is added to 1 ml of the THF extract to obtain a sample for analyzing the surface oligomers.
[0040]
- HPLC Analysis -
The sample for analyzing the content of all the oligomers or the sample for analyzing the surface oligomers can be used to perform HPLC analysis under the following HPLC conditions.
[0041]
[HPLC Conditions]
- HPLC device: ACQUITY UPLC H-Class system (manufactured by WATERS)
- Column: ACQUITY UPLC BEH C18 (manufactured by WATERS, column: 50 x 2.1 mm
I D., particle diameter: 1.7 pm)
- Column temperature: 40°C
- Mobile phase: Phase A: 10 mM aqueous solution of ammonium formate, Phase B: acetonitrile - Gradient conditions:
- 0 minutes to 5 minutes: 99/1 (phase A/phase B, volume ratio)
- 5 minutes to 6.25 minutes: 1/99 (phase A/phase B, volume ratio)
- 6.25 minutes to 7.5 minutes: 1/99 (phase A/phase B, volume ratio)
- 7.5 minutes and longer: 99/1 (phase A/phase B, volume ratio)
- Volume of injected sample: 5 pL
- Sample temperature: 10 °C
- UV conditions: Capture wavelength: 195 nm to 480 nm, resolution: 1.2 nm [0042]
- Quantitative Analysis of Oligomers -
When the base material is polyethylene terephthalate (PET) in a method of calculating a quantitative value from the peak area in HPLC, the quantitative value of the cyclic trimer of dimethyl phthalate (CDMP), which is the oligomer to be measured, can be converted from the quantitative value of dimethyl phthalate (DMP).
[0043]
Specifically, a calibration curve for dimethyl phthalate is calculated from the measurement results of a standard solution of DMP. To obtain a standard solution, about 60 mg of dimethyl phthalate is dissolved and diluted with acetonitrile in a 50 ml measuring flask to prepare a DMP standard solution having a known concentration of 1200 ppm, which is then progressively diluted and used. The content in terms of DMP is calculated from the peak area in HPLC corresponding to the oligomers. Subsequently, the content in terms of DMP is converted into the content of CDMP, assuming that the molar absorption coefficient of CDMP is three times the molar absorption coefficient of DMP.
[0044]
<Surfactant>
The functionalized base material is substantially free of surfactants. Here, “substantially free” means that, when the functionalized base material is extracted with tetrahydrofuran (THF) and components thereof are analyzed, the content of surfactants to be evaluated is below the detection limit.
[0045]
Here, in conventional dyeing using water, water containing a dye, a dispersant, and the like is used in the dyeing process. Also, a large amount of water containing a surfactant, a reducing agent, and the like is used in a washing process. Thus, a large amount of waste liquid to be treated is produced, and a large amount of energy is required for drying, so that the environmental impact is extremely high. According to the method of manufacturing a functionalized base material and the functionalized base material of the present embodiment, no large amount of dye adheres to the surface of a base material such as fibers. Therefore, there is no need to perform soaping by using a surfactant or the like, and no additives such as a dispersant are required. Thus, chemicals such as surfactants or large amounts of water are not used, and further, the functionalized base material is substantially free of surfactants. [0046]
Specifically, the THF extract of the functionalized base material and the sample used for analyzing the components can be obtained by the following procedure. A part (about 0.01 g) of the functionalized base material is separated to be used as an evaluation sample. The evaluation sample is placed in a 1.5 ml vial, and about 1.2 g of THF is added to the vial. The mixture is treated with ultrasonic waves at 40 KHz for 30 minutes at an initial temperature of 25°C, and then allowed to stand one night to obtain a THF extract. The obtained THF extract is diluted about 10-fold with acetonitrile and fdtered through a 0.45 pm PTFE fdter to obtain a sample for analyzing the components.
[0047]
Specifically, to analyze the components in the THF extract of the functionalized base material and confirm that the THF extract is substantially free of surfactants, LC-MS analysis can be performed under the following LC-MS conditions and MS conditions, to confirm that no peak is detected for the surfactants being measured.
[0048]
[LC-MS Conditions]
- Mass spectrometer: micrOTOF-QII (manufactured by Bruker Daltonics Inc.)
- UHPLC device: NEXERA XR (manufactured by Shimadzu Corporation)
- Column: YMC-TRIART C18 (manufactured by YMC Co., Ltd., column: 50 x 2.1 mm I.D., particle diameter: 1.9 pm, pore size: 12 nm)
- Column temperature: 40°C
- Mobile phase: Phase A: 10 mM aqueous solution of ammonium formate, Phase B: acetonitrile
- Gradient conditions:
- 1 minute to 10 minutes: 60/40 (phase A/phase B, volume ratio)
- 10 minutes to 15 minutes: 2/98 (phase A/phase B, volume ratio) - 15 minutes to 20 minutes: 60/40 (phase A/phase B, volume ratio)
- Volume of injected sample: 10 pL
- Ionization method: electro spray ionization (ESI)
- Detected ions: Positive ions
- Source:
- End plate offset: -500 V
- Capillary: 4500 V
- Nebulizer: 2.0 bar
- Drying gas: 8.0 L/min
- Drying temperature: 200°C
- Calibration: Tuning mix ES-TOF (ESI) (manufactured by Agilent Technologies) [0049]
[MS Conditions]
- Mode: Wide - Funnel 1: 300 Vpp
- Funnel 2: 300 Vpp
- Hexapole: 300 Vpp
- Collision RF: 600 Vpp
- Transfer time: 120 ps
- Pre pulse storage: 8 ps [0050]
The functionalized base material preferably includes the functionalizing agent inside the functionalized base material. Here, it can be confirmed that the functionalized base material “includes” the functionalizing agent “inside” the functionalized base material by, for example, evaluating the washing fastness and the rubbing fastness to confirm if the functionalizing agent such as a dye does not elute or detach from the functionalized base material. Specifically, in the evaluation, it is possible to evaluate whether a material satisfies at least any one of (1) to (3) below, and it is preferable to evaluate whether a material satisfies all of
(1) to (3) below.
(1) A discoloration degree evaluated by a washing fastness test according to Japanese Industrial Standards (JIS) L 0844 No. A-2 is grade 4 or higher.
(2) A staining degree evaluated by a washing fastness test according to JIS L 0844 No. A-2 is grade 3 or higher.
(3) A staining degree evaluated by a rubbing fastness test that is a dry test according to the rubbing tester type II method (Gakushin-type method) of JIS L 0849 is grade 3 to 4 or higher. [0051]
Note that, JIS L 0844 No. A-2 corresponds to Test 2B(2) of the international standard ISO 105-C10, and JIS L 0849 corresponds to the international standard ISO 105-X12, and thus, each evaluation can be performed in accordance with the corresponding standards.
[0052]
Further, examples of a method of evaluating whether the functionalized base material contains a functionalizing agent other than a dye therein include a method of comparing the content of the functionalizing agent in the functionalized base material after the washing test for the washing fastness with the content of the functionalizing agent in a control functionalized base material that is not subjected to the washing test; and a method of comparing the content of the functionalizing agent in the functionalized base material after the rubbing test for the rubbing fastness with the content of the functionalizing agent in a control functionalized base material that is not subjected to the rubbing test. A method of quantifying the content of the functionalizing agent can be appropriately selected in accordance with the type of the functionalizing agent being used. The ratio of the content (Ci) of the functionalizing agent in the functionalized base material after the washing test or the rubbing test relative to the content (Co) of the functionalizing agent in the control functionalized base material, that is, (Ci/Co) * 100 (mass%), is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more. [0053]
(Apparatus for Manufacturing Functionalized Base Material)
An apparatus for manufacturing a functionalized base material of the present embodiment includes a high-pressure vessel used for mixing a supercritical fluid and a functionalizing agent, and a pulse valve used for discharging, in a gas phase state and/or a supercritical state, the supercritical fluid that is supplied from the high-pressure vessel and in which the functionalizing agent is dissolved, and further includes other components, if desired. Embodiments for implementing the disclosure will be described below with reference to the drawings. In the drawings, the same constituent components are denoted by the same reference numerals, and overlapping parts of the description may be omitted.
[0054]
A functionalized base material manufacturing apparatus 1 according to the present embodiment will be described with reference to FIG. 1.
FIG. 1 is a schematic diagram illustrating a functionalized base material manufacturing apparatus according to the present embodiment. The functionalized base material manufacturing apparatus 1 includes a generation unit 30 that generates a supercritical fluid, a supply unit 40 that supplies a functionalizing agent, a high-pressure vessel 6 used for mixing the supercritical fluid generated in the generation unit 30 with the functionalizing agent supplied from the supply unit 40 to obtain a mixture 20 of the two substances, a pulse valve 10 that discharges the mixture 20 supplied from the high-pressure vessel 6 onto a base material 12, and a pipe 51 that connects the high-pressure vessel 6 and the pulse valve 10. Further, the mixture 20 of the supercritical fluid and the functionalizing agent may be simply referred to as “mixture”.
[0055]
As illustrated in FIG. 1, the generation unit 30 includes a gas cylinder 3 storing liquid carbon dioxide, a cooler 31 used for cooling the liquid carbon dioxide supplied from the gas cylinder 3 via a high-pressure valve 101 to a temperature below the saturation temperature, a high- pressure pump 32 that pressurizes the liquid carbon dioxide to a predetermined pressure, a heater 33 used for heating the liquid carbon dioxide supplied from the high-pressure pump 32 to a predetermined temperature, and a back pressure valve 102 that returns excess liquid carbon dioxide from the liquid carbon dioxide supplied from the high-pressure pump 32 to the downstream side of the high-pressure pump 32.
[0056]
An example of the cooler 31 includes a chiller device that causes cooling water to circulate to cool an object to be cooled. Moreover, an example of the high-pressure pump 32 includes a double plunger pump by which it is possible to control the discharge amount of liquid and prevent pulsation. However, the cooler 31 and the high-pressure pump 32 are not limited to the examples mentioned above.
[0057] Liquid carbon dioxide that is pressurized by the high-pressure pump 32 is heated by the heater 33 to vaporize the carbon dioxide. The vaporized carbon dioxide is introduced into the high- pressure vessel 6 and heated and pressurized to bring the carbon dioxide into a supercritical state.
[0058]
As illustrated in FIG. 1, the supply unit 40 includes a container 4 storing a functionalizing agent and, if desired, an entrainer, a high-pressure pump 41 that pressurizes the functionalizing agent supplied from the container 4 via a high-pressure valve 106 to a predetermined pressure, and a heater 42 used for heating the functionalizing agent supplied from the high-pressure pump 41 to a predetermined temperature.
[0059]
The high-pressure vessel 6 mixes, under conditions including high pressure, the supercritical fluid supplied from the generation unit 30 via a high-pressure valve 103 and the functionalizing agent supplied from the supply unit 40 via a high-pressure valve 107. An example of the high-pressure vessel 6 is an autoclave. However, the high-pressure vessel 6 is not limited thereto.
[0060]
The high-pressure vessel 6 includes a vessel main body 21 containing a supercritical fluid and a functionalizing agent, a stirring mechanism 22 that stirs the supercritical fluid and the functionalizing agent introduced into the vessel main body 21, a motor 7 that drives the stirring mechanism 22, and a torque meter 23 that measures the rotational force of the stirring mechanism 22.
[0061]
Examples of the stirring mechanism 22 include a magnetic impeller (an impeller that rotates by the driving force from a motor), a single-shaft screw, a twin-shaft screw with an intermeshing structure, a twin- shaft mixer having a large number of intermeshing or overlapping stirring elements, a kneader having intermeshing helical stirring elements, and a static mixer. Moreover, the high-pressure vessel 6 preferably further includes a heater 8 used for heating a vessel.
[0062]
In an initial stage of mixing the supercritical fluid and the functionalizing agent in the high- pressure vessel 6, the supercritical fluid and the functionalizing agent are not sufficiently mixed. Therefore, the viscosity of the mixture may be high and the torque of the stirring mechanism 22 may be high. However, as the mixing of the supercritical fluid and the functionalizing agent progresses, the viscosity of the mixture decreases. Accordingly, the torque of the stirring mechanism 22 also decreases. Further, when the supercritical fluid and the functionalizing agent are sufficiently mixed with each other, the viscosity of the mixture further decreases. Afterwards, the viscosity stops decreasing. Accordingly, the torque of the stirring mechanism 22 becomes constant. That is, when the torque meter 23 detects that the torque of the stirring mechanism 22 is constant, it can be determined that the supercritical fluid and the functionalizing agent are sufficiently mixed.
[0063]
In the high-pressure vessel 6, the supercritical carbon dioxide fluid and the functionalizing agent are mixed under high pressure, for example, under a pressure of about 40 MPa to 50 MPa. Here, such a state in which the supercritical carbon dioxide fluid and the functionalizing agent are mixed preferably refers to a state in which the supercritical carbon dioxide fluid and the functionalizing agent are dissolved. Therefore, it is generally not possible to visually check the progress of mixing of the supercritical carbon dioxide fluid and the functionalizing agent by, for example, opening the lid of the high-pressure vessel 6. However, if the torque meter 23 is used to measure the change of the torque in the stirring mechanism 22, it is possible to determine whether the supercritical carbon dioxide fluid and the functionalizing agent are uniformly mixed without visually inspecting the inside of the high-pressure vessel 6. As a result, it is possible to prevent unmixed functionalizing agent from being supplied to the pulse valve 10, and discharge defects of the pulse valve 10 can be prevented.
[0064]
The torque meter 23 may output a torque measurement signal of the stirring mechanism 22 to a control device 24. Further, the control device 24 may determine whether the supercritical fluid and the functionalizing agent are uniformly mixed, based on a torque measurement signal from the torque meter 23. Moreover, the control device 24 may control an opening and closing process of a high-pressure valve 104 arranged downstream of the high-pressure vessel 6, based on the determination result.
[0065]
The high-pressure valve 104 and a high-pressure valve 105 are provided downstream of the high-pressure vessel 6 in the flow path. The high-pressure valve 104 is provided above the high-pressure vessel 6. By adjusting the supercritical state of the high-pressure vessel 6, it is possible to selectively extract only a gas phase portion from the high-pressure valve 104, even in a gas-liquid equilibrium state.
Further, the high-pressure valve 105 is provided below the high-pressure vessel 6, and a liquid phase portion can be extracted from the high-pressure valve 105, or a waste liquid containing the functionalizing agent can be transferred to a waste liquid tank 9 via a pipe 52.
[0066]
When the high-pressure valve 104 opens, the mixture in the high-pressure vessel 6 passes through the pipe 51 and is supplied to the pulse valve 10. It is preferable to provide a heating mechanism or a heat insulating member around the pipe 51. Thus, the pipe 51 can be maintained at a predetermined temperature. As a result, the supercritical state of the carbon dioxide flowing through the pipe 51 can be maintained, while the supercritical fluid in which the functionalizing agent is dissolved can be conveyed and discharged in a gas phase state and/or a supercritical state. [0067]
The pulse valve 10 is connected to a front end of the pipe 51. Thus, the pulse valve 10 and the pipe 51 communicate with each other, and the mixture flowing through the pipe 51 is introduced into the pulse valve 10. The pulse valve 10 discharges the introduced mixture in a gas phase state and/or a supercritical state to the base material 12. [0068]
The base material 12 is placed on a conveyance mechanism 14, and the position of the base material 12 relative to the pulse valve 10 can be controlled by the conveyance mechanism 14, such as a stage. The conveyance mechanism 14 may further include or separately include a heating mechanism 15. The heating mechanism 15 heats the base material 12 to a predetermined temperature. Examples of the heating mechanism 15 include a heater, a hot air generation device, and a laser for localized heating. According to such a configuration, the amount of the functionalizing agent to be applied to each application region of the base material 12 can be controlled by adjusting the discharge amount and the conveyance speed. Thus, it is possible to apply the functionalizing agent to specific regions of the base material, and to implement differentiated dyeing and image formation.
[0069]
For example, a mixture having a temperature of more than 150°C (for example, a temperature of 170°C) and a pressure of about 40 MPa to 50 MPa is introduced into the pulse valve 10. The pulse valve 10 discharges the mixture in a gas phase state and/or a supercritical state toward the base material 12, while maintaining the temperature and the pressure of the mixture at the time of introduction of the mixture. The pulse valve 10 performs high-speed opening and closing operations, so that the opening time is 100 psec or less, for example. Thus, the pulse valve 10 can stably discharge a desired amount of the mixture. Note that the pulse valve 10 will be described in detail in the section < Configuration of Pulse Valve> below.
[0070]
[Operation of Functionalized Base Material Manufacturing Apparatus 1]
An operation of discharging a mixture in the functionalized base material manufacturing apparatus 1 will be described with reference to FIG. 1. First, liquid carbon dioxide stored in the gas cylinder 3 passes through the high-pressure valve 101 and is cooled to a temperature equal to or lower than the saturation temperature in a cooler 31.
[0071]
Subsequently, the supercritical carbon dioxide fluid passing through the cooler 31 is introduced into a suction portion of the high-pressure pump 32. The liquid carbon dioxide introduced into the high-pressure pump 32 from the suction portion is pressurized in the high- pressure pump 32 to a predetermined pressure (such as 7.3 MPa, which is the critical pressure of carbon dioxide) or higher. During operation at constant pressure, the liquid carbon dioxide introduced into the high-pressure pump 32 is returned to the suction portion of the high- pressure pump 32 by the back pressure valve 102. [0072]
Subsequently, the heater 33 heats the pressurized liquid carbon dioxide to a predetermined temperature (such as 31 °C, which is the critical temperature of carbon dioxide) or higher. Thus, supercritical carbon dioxide is generated from liquid carbon dioxide.
[0073]
Next, the generated supercritical carbon dioxide fluid is introduced via the high-pressure valve 103 into the high-pressure vessel 6 which is heated to a predetermined temperature by the heater 8. The stirring mechanism 22 connected to the motor 7 melts and mixes the supercritical carbon dioxide fluid and a functionalizing agent introduced into the high- pressure vessel 6 via a separate path.
[0074]
At this time, the heater 8 heats the mixture to about 170°C, for example. The mixture is pressurized to, for example, about 40 MPa to 50 MPa by a predetermined pressure increasing mechanism.
[0075]
In the present embodiment, the mixture of the supercritical carbon dioxide and the functionalizing agent is obtained by these mixing processes. It is possible to determine whether a uniform mixture is obtained, based on the measurement value of the torque meter 23 measuring the torque of the stirring mechanism 22.
[0076]
Subsequently, the high-pressure valve 104 is opened. Thus, the mixture in the high-pressure vessel 6 passes through the pipe 51 and flows toward the pulse valve 10. The pulse valve 10 maintains the temperature and the pressure of the mixture introduced into the pulse valve 10, while repeatedly opening and closing the valves provided within the pulse valve 10 to discharge a desired amount of the mixture onto the base material 12.
[0077]
Configuration of Pulse Valve>
Next, a configuration of the pulse valve 10 of the functionalized base material manufacturing apparatus 1 will be described with reference to FIGs. 2 and 3. FIGs. 2 and 3 are vertical cross-sectional views of the pulse valve 10.
[0078]
As illustrated in FIG. 2, the pulse valve 10 includes a housing unit 110 having a flow path 112 therein for a fluid to be discharged, a nozzle unit 120 attached to a front end side of the housing unit 110 and discharging the fluid to be discharged, a needle 130 that is inserted into the housing unit 110 and opens and closes the flow path 112 of the housing unit 110, a drive mechanism 140 that reciprocates the needle 130, and a heat insulating flange 150 provided between the housing unit 110 and the drive mechanism 140. The fluid to be discharged in the present embodiment is a mixture of a supercritical fluid and a functionalizing agent.
[0079] Here, an X direction in the drawings corresponds to a front-rear direction of the pulse valve 10. A Y direction corresponds to a width direction of the pulse valve 10. Further, a Z direction corresponds to a height direction of the pulse valve 10.
[0080]
<<Housing Unit>>
The housing unit 110 is located at a frontmost portion of the pulse valve 10 and is formed by a case accommodating a mixture introduced from a pipe 441. A front end surface (a frontmost surface on a + side in the X direction) of the housing unit 110 faces the base material 12.
[0081]
The housing unit 110 includes a base portion 111. The flow path 112 for the mixture to be discharged is formed inside the base portion 111. In the present embodiment, the flow path 112 is formed along the X direction. Further, a first hole portion 113 is formed as a recess in an upper surface (an uppermost surface at the + side of the Z direction) of the base portion 111 so as to be recessed toward the flow path 112. The 1/8 inch pipe 441 attached to the front end of the pipe 51 is inserted into the first hole portion 113. The 1/8 inch pipe 441 inserted into the first hole portion 113 communicates with the flow path 112. Note that, the pipe 51 and the 1/8 inch pipe 441 may be collectively referred to as “pipe 51”. Thus, the mixture flowing through the pipe 51 is introduced into the flow path 112. However, the pipe communicating with the flow path 112 may be a pipe having a size or shape different from the 1/8 inch pipe.
[0082]
The first hole portion 113 includes a tapered portion 113T having a diameter that decreases towards the - side in the Z direction, which is the side of the flow path 112. Further, it is preferable that the 1/8 inch pipe 441 is fitted into the first hole portion 113 via a connection ferrule that is deformed by pressure when contacting the tapered portion 113T of the first hole portion 113. A mixture having a high temperature and high pressure flows through the 1/8 inch pipe 441. Therefore, by fitting the 1/8 inch pipe 441 into the first hole portion 113 via the connection ferrule, the 1/8 inch pipe 441 does not detach from the first hole portion 113, even when a mixture having a high temperature and high pressure flows through the 1/8 inch pipe 441.
[0083]
A region of the base portion 111 where the first hole portion 113 is provided may be heated by a heating mechanism (for example, a heating block). By providing a heating mechanism, it is possible to prevent a decrease in the temperature of the mixture flowing through the 1/8 inch pipe 441.
[0084]
The housing unit 100 includes a block 114 on the front end side (the + side in the X direction) from the base portion 111. The block 114 is attached to the base portion 111 via screws 115a and 115b. [0085]
A second hole portion 116 is formed as a recess in a front end surface of the block 114 (that is, a front end surface of the housing unit 110) and is recessed toward the - side in the X direction, which is the side of the flow path 112. The second hole portion 116 of the present embodiment is formed along the X direction. The nozzle unit 120 is inserted into the second hole portion 116.
The second hole portion 116 is an example of a “hole portion”.
[0086]
The pressure of the mixture accommodated in the housing unit 110 is preferably 60 MPa or less. The temperature of the mixture accommodated in the housing unit 110 is preferably 250°C or less. However, the pressure and the temperature of the mixture are not limited thereto.
[0087]
<<Nozzle Unit>>
The nozzle unit 120 includes a nozzle base portion 121 that extends along the X direction when the nozzle unit 120 is inserted into the second hole portion 116. A pressure-type connection screw is formed on an outer peripheral portion of the nozzle base portion 121. A thread groove of the connection screw in the nozzle base portion 121 engages with a thread groove formed in the second hole portion 116, so that the nozzle unit 120 is fitted into the second hole portion 116 while being pressed.
[0088]
A nozzle pipe portion 122 having a tube shape along the X direction is formed inside the nozzle base portion 121. As illustrated in FIG. 3, the nozzle pipe portion 122 includes a first pipe portion 122a communicating with the front end of the flow path 112, and a second pipe portion 122b that is concentric with the first pipe portion 122a and is provided outside the first pipe portion 122a. The front end of the second pipe portion 122b corresponds to a nozzle hole 123 through which the mixture is discharged onto the base material 12.
[0089]
The nozzle pipe portion 122 has a double pipe structure including the first pipe portion 122a and the second pipe portion 122b. By using such a double pipe structure, the strength of the nozzle pipe portion 122 can be increased. Further, the discharge stability of the mixture supplied from the flow path 112 can be improved.
[0090]
The diameter of the nozzle hole 123 is preferably 5 pm or more and 500 pm or less. The diameter of the nozzle hole 123 is more preferably 100 pm or more and 300 pm or less, and even more preferably 150 pm or more and 250 pm or less.
[0091]
The diameter of the nozzle hole 123 preferably is not less than 5 pm, because in this case, the diameter is too small and the mixture may not be stably discharged. The diameter of the nozzle hole 123 preferably does not exceed 500 pm, because in this case, the thickness of a region of the nozzle unit 120 excluding the nozzle hole 123 is thin, and the nozzle hole 123 may not withstand the pressure when the mixture is discharged.
[0092]
The nozzle unit 120 also includes a connection ferrule 124 provided on an outer peripheral portion of the nozzle pipe portion 122. For example, as illustrated in FIGs. 2 and 3, the connection ferrule 124 is a member made of stainless steel, which substantially has a truncated cone shape of which a diameter decreases toward the - side in the X direction. [0093]
When the nozzle unit 120 is fitted into the second hole portion 116 in a pressed state, the connection ferrule 124 collides with a tapered portion 116 T of the second hole portion 116. After colliding with the tapered portion 116T, the connection ferrule 124 moves further into the second hole portion 116 and is inserted into the inside of the tapered portion 116T. As a result, the connection ferrule 124 is pressed and deformed by being pressed against the tapered portion 116T of the second hole portion 116. This restricts further movement of the connection ferrule 124. As a result, the nozzle unit 120 is fitted into the second hole portion 116 and firmly fixed to the block 114.
[0094]
The nozzle unit 120 is fixed to the block 114 of the housing unit 110 via the connection ferrule 124, and thus, it is possible to improve the pressure resistance and the durability. In particular, a mixture having high pressure flows through the nozzle unit 120, and thus, it is preferable to join the nozzle unit 120 and the housing unit 110 via the connection ferrule 124. [0095] <<Needle>>
The needle 130 is inserted into the housing unit 110 and functions as a valve that opens and closes the flow path 112 of the housing unit 110.
[0096]
Specifically, as the needle 130 moves forward, a front end of the needle 130 closes an extremely small hole 132 of an orifice 131 provided between the flow path 112 and a rear end of the nozzle pipe portion 122 of the nozzle unit 120. Thus, the flow path 112 is closed. Subsequently, the needle 130 retracts, and the front end of the needle 130 moves away from the orifice 131. Therefore, the extremely small hole 132 of the orifice 131 is opened, and the flow path 112 opens.
[0097]
When the needle 130 opens and closes the flow path 112, a desired amount of the mixture that reaches the flow path 112 can be supplied toward the nozzle unit 120. The response speed of the needle 130 (opening time of the valve) is preferably 100 psec or less.
[0098]
<<Drive Mechanism>>
The drive mechanism 140 is a mechanical unit that is connected to the needle 130 and reciprocates the needle 130. Specifically, as illustrated in FIG. 2, the drive mechanism 140 includes an extension bar 141 having an elongated tubular shape that is connected to a rear end of the needle 130, and a piezoelectric actuator 142 that reciprocates the extension bar 141 at a predetermined speed.
[0099]
The extension bar 141 is preferably made of a material having a low coefficient of thermal expansion to avoid thermal expansion due to heat transfer from the needle contacting the mixture. Examples of materials having a low coefficient of thermal expansion include, but are not limited to, INVAR, which is an alloy of iron and nickel, and SUPER INVAR, which is an alloy of iron, nickel, and cobalt. Among these materials, SUPER INVAR, which has an extremely low coefficient of thermal expansion, is preferable.
[0100]
For example, a mixture having a temperature of about 250°C flows through the flow path 112. A front end region of the needle 130 is inserted into the flow path 112 and contacts the mixture. The extension bar 141, on the other hand, is continuously provided with the needle 130. Therefore, heat is transferred from the mixture to the extension bar 141 via the needle 130. At this time, if the extension bar 141 strongly expands by thermal expansion, the range of the reciprocating movement of the extension bar 141 changes, and the range of the reciprocating movement of the needle 130 also changes. As a result, it may not be possible to accurately supply a desired amount of the mixture contained in the flow path 112 toward the nozzle unit 120. In contrast, if the extension bar 141 is made of a material having a low coefficient of thermal expansion, such as SUPER INVAR, thermal expansion of the extension bar 141 can be suppressed, even if heat from the mixture is transferred from the needle 130. As a result, a desired amount of the mixture can be accurately supplied toward the nozzle unit 120.
[0101]
Further, by forming the extension bar 141 from a material that suppresses thermal expansion, such as SUPER INVAR, the operational stability of the piezoelectric actuator 142 can be ensured.
[0102]
For example, the piezoelectric actuator 142 includes a piezoelectric element that deforms by expanding and contracting in response to the application of a pulse- shaped voltage signal. In the present embodiment, the piezoelectric actuator 142 deforms by expanding and contracting in the X direction. The piezoelectric actuator 142 is preferably a ring actuator provided around the outer periphery of the extension bar 141. By using a ring actuator as the piezoelectric actuator 142, the piezoelectric actuator 142 has no sharp corner portions and the load during operation is distributed evenly over the entire surface of the piezoelectric actuator 142, so that the durability can be improved. Further, the piezoelectric actuator 142 can be formed from a thin piezoelectric element layer, and thus, a large amount of displacement can be obtained at a low voltage. [0103] In the present embodiment, the piezoelectric actuator 142 is used as the actuator of the drive mechanism 140, but other types of actuators may also be used. However, the piezoelectric actuator 142 is preferably used to achieve a high-speed response in which the valves are opened and closed in less than about 100 psec.
[0104]
<<Heat Insulating Flange>>
The heat insulating flange 150 prevents heat transfer from the housing unit 110 toward the piezoelectric actuator 142. The material of the heat insulating flange 150 is not particularly limited, but is preferably made of a ceramic having high heat insulating properties. By providing the heat insulating flange 150 between the housing unit 110 and the piezoelectric actuator 142, it is possible to prevent heat from being transferred from the mixture to the piezoelectric actuator 142, which is sensitive to heat. As a result, the operational stability of the piezoelectric actuator 142 can be ensured.
[0105]
Next, a pulse valve 10a according to a second embodiment will be described with reference to FIGs. 4 and 5.
FIG. 4 is a vertical cross-sectional view of the pulse valve 10a according to the second embodiment. FIG. 5 is a cross-sectional view of the pulse valve 10a taken along line A-A indicated in FIG. 4.
[0106]
As illustrated in FIG. 5, the flow path 112 includes a plurality of divided paths 112a to 112d each extending along the X direction. The positions of the divided paths 112a to 112d are not particularly limited, but are preferably in a front end region in the vicinity of the orifice 131 in the flow path 112.
[0107]
The divided paths 112a to 112d are arranged along the circumferential direction of the needle 130 and are formed by gaps extending outward in a radial direction from an outer peripheral wall 135 of the needle 130. Further, boundary walls of adjacent divided paths, such as a boundary wall between the divided path 112a and the divided path 112b, a boundary wall between the divided path 112b and the divided path 112c, a boundary wall between the divided path 112c and the divided path 112d, and a boundary wall between the divided path 112d and the divided path 112a, contact the outer peripheral wall 135 of the needle 130. Thus, the needle 130 can be guided so as to be positioned at the center of the flow path 112, even after the needle 130 reciprocates. As a result, a desired amount of the mixture can be accurately supplied toward the nozzle unit 120.
[Examples]
[0108]
The present disclosure will be described in more detail below based on Examples. However, the present disclosure is not limited to the Examples described below.
[0109] (Example 1)
A PET knit (manufactured by Uni Textile Co., Ltd., fabric weight: 138 g/m2, yarn count: 75/72) was used as a fabric-like base material to which a functionalizing agent was to be applied. The dye Disperse Blue 14 was used as the functionalizing agent.
[0110]
The functionalized base material manufacturing apparatus 1 illustrated in FIG. 1 was used to supply 5 mg of Disperse Blue 14 to the high-pressure vessel 6 having a volume of 400 ml at a temperature of 135°C and a pressure of 40 MPa, and the dye was dissolved in a supercritical carbon dioxide fluid. The base material was cut to a size of 8 cm x 10 cm, placed on the stage of the conveyance mechanism 14, and heated to a surface temperature of 150°C by the heating mechanism 15. Next, while the base material was being conveyed at a speed of 15 mm/sec, the supercritical carbon dioxide fluid in which Disperse Blue 14 was dissolved was discharged in a gas phase state and/or a supercritical state from the pulse valve 10 having the nozzle hole 123 with a diameter of 100 pm, and applied to the base material. To prevent a temperature decrease due to gas expansion when discharging the supercritical carbon dioxide fluid, the pulse valve 10 was heated and maintained at 145°C, and the base material was dyed by maintaining the heated state for 10 minutes. Thus, a functionalized base material of Example 1 was prepared.
[0111]
(Comparative Example 1)
The base material used in Example 1, that is, an undyed fabric, was used as the functionalized base material in Comparative Example 1.
[0112]
(Comparative Example 2)
14 g of the base material was placed inside the high-pressure vessel 6 having a volume of 400 ml in the functionalized base material manufacturing apparatus 1 illustrated in FIG. 1. 42 mg of Disperse Blue 14 and supercritical carbon dioxide fluid were supplied to the high-pressure vessel 6 and mixed, so that the temperature was 120°C and the pressure was 25 MPa. The base material was dyed for 60 minutes at a bath ratio of 1:28 (mass ratio), and thus, a functionalized base material of Comparative Example 2 was prepared.
[0113]
(Comparative Example 3)
10 g of the base material was placed in a high-pressure vessel having a volume of 400 ml in a mini color dyeing machine (manufactured by Texam Co., Ltd.). A suspension in which 30 mg of Disperse Blue 14 were suspended in 300 mL of water was used to dye the base material at 130°C for 60 minutes at a bath ratio of 1:30 (mass ratio). After dyeing, the obtained base material was reduced and cleaned at 80°C for 20 minutes in an aqueous solution containing 1 g of a concentrated solution of SUNMORL RC-700E (manufactured by Nicca Chemical Co., Ltd.), which is used as a surfactant or soaping agent, 2 g of hydrosulfite, and 2 g of NaOH with respect to 1 L of water, to prepare a functionalized base material of Comparative Example 3.
[0114]
<Evaluation>
In each functionalized base material, the measurement of surface oligomers and the measurement of total oligomers was evaluated by the following procedures.
[0115]
<Measurement of Surface Oligomers > << Extraction with Tetrahydrofuran >>
Each functionalized base material was cut into a size of 1 cm x 1 cm to be used as an evaluation sample. Each evaluation sample was divided into four equal pieces. One piece was placed in a 10 ml vial, and about 5 ml of tetrahydrofuran (THF) was added. The mixture was treated with ultrasonic waves at 40 KHz for 30 minutes at an initial temperature of 25°C, and then allowed to stand one night to obtain a THF extract. About 9.5 ml of acetonitrile was added to 1 ml of the THF extract to obtain a sample for analyzing the surface oligomers. The oligomers extracted by the above-described extraction with tetrahydrofuran were defined as oligomers present on the surface of the functionalized base material, and were subsequently subjected to HPLC analysis.
[0116]
<<HPLC Analysis >>
The sample for analyzing the surface oligomers was analyzed by HPLC under the following HPLC conditions.
[0117]
[HPLC Conditions]
- HPLC device: ACQUITY UPLC H-Class system (manufactured by WATERS)
- Column: ACQUITY UPLC BEH C18 (manufactured by WATERS, column: 50 x 2.1 mm
I D., particle diameter: 1.7 pm)
- Column temperature: 40°C
- Mobile phase: Phase A: 10 mM aqueous solution of ammonium formate, Phase B: acetonitrile
- Gradient conditions:
- 0 minutes to 5 minutes: 99/1 (phase A/phase B, volume ratio)
- 5 minutes to 6.25 minutes: 1/99 (phase A/phase B, volume ratio)
- 6.25 minutes to 7.5 minutes: 1/99 (phase A/phase B, volume ratio)
- 7.5 minutes and longer: 99/1 (phase A/phase B, volume ratio)
- Volume of injected sample: 5 pL
- Sample temperature: 10 °C
- UV conditions: Capture wavelength: 195 nm to 480 nm, resolution: 1.2 nm [0118]
<< Quantitative Analysis of Oligomers>> In a method of calculating a quantitative value from the peak area in HPLC, the quantitative value of the cyclic trimer of dimethyl phthalate (CDMP), which is the oligomer to be measured, was converted from the quantitative value of dimethyl phthalate (DMP). [0119]
Specifically, a calibration curve for dimethyl phthalate was calculated from the measurement results of a standard solution of DMP. To obtain the standard solution, about 60 mg of dimethyl phthalate was dissolved and diluted with acetonitrile in a 50 ml measuring flask to prepare a DMP standard solution having a known concentration of 1200 ppm, which was then progressively diluted and used. The content in terms of DMP was calculated from the peak area in HPLC corresponding to the oligomers. Subsequently, the content in terms of DMP was converted into the content of CDMP, assuming that the molar absorption coefficient of CDMP is three times the molar absorption coefficient of DMP. The content of oligomers on the surface of each of the obtained functionalized base materials is indicated in Table 1. [0120]
< Measurement of Total Oligomers > The total oligomers in each functionalized base material were measured as follows. Each functionalized base material was completely dissolved in hexafluoroisopropanol and the polymers were precipitated with acetonitrile. Subsequently, the precipitate was filtered through a filter to obtain an extract. The obtained extract was used in the analysis of the oligomers in the entire functionalized base material.
[0121]
<< Extraction with Hexafluoropropanol>>
Each evaluation sample was divided into four equal pieces, one of which was placed in a 10 ml vial, and about 0.6 ml of hexafluoropropanol was added to the vial. The vial was left standing for about 2 hours, and then, about 9.4 ml of acetonitrile was added. The obtained mixture was filtered through a PTFE filter having a pore size of 0.2 pm to obtain a sample for HPLC analysis.
[0122]
<< Quantitative Analysis of Total Oligomers>>
The obtained extract was used to implement the above-described <<HPLC Analysis >> and << Quantitative Analysis of Oligomers>> to calculate the total oligomer content in each functionalized base material. The results are illustrated in Table 1.
[0123] [Table 1]
[0124]
The results in Table 1 indicate that, in the batch-type waterless dyeing of Comparative Example 2, the content of surface oligomers was higher than in Example 1 and Comparative Example 3. In Comparative Example 2 (batch-type waterless dyeing), oligomers were eluted from inside the base material during the batch dyeing. Further, when the pressure was released from the batch after dyeing, the solubility of the oligomers in carbon dioxide decreased. Therefore, the oligomers were re-fixed to the surface of the base material or migrated and moved, which is considered to be the cause of the above-mentioned phenomenon.
[0125]
When the water dyeing of Comparative Example 3 is compared with the dyeing using the application step of Example 1, the content of surface oligomers is not much different, but the content of internal oligomers is different by 0.15 mass%. In Comparative Example 3 (water dyeing), oligomers elute from inside the base material, similarly to Comparative Example 2, but the amount of elution is smaller than in Comparative Example 2. In addition, in Comparative Example 3 (water dyeing), the dye liquor was removed in a state where the oligomers were dissolved in the dye liquor, so that the oligomers were less likely to be refixed to the surface of the functionalized base material. The increase (re-fixation) of surface oligomers was suppressed, and at the same time, it is considered that the content of internal oligomers was also reduced.
[0126]
On the other hand, in the dyeing using the application step of Example 1, the oligomers migrate due to heating. However, it was found that the oligomers are unlikely to be eluted by the carbon dioxide fluid, because the carbon dioxide density is low when the carbon dioxide fluid is applied to the base material. Therefore, the amount of oligomers moving to the surface of the functionalized base material (content of surface oligomers) is small.
[0127]
<Detection of Surfactant>
Surfactants were detected in the (water dyed) functionalized base material of Comparative Example 3 by the following procedure.
On the other hand, in Example 1, the base material was not treated with a surfactant, and thus, no surfactant would be detected. This confirmed that, when a surfactant is used, the surfactant can be distinguished from the components adhering to the fabric.
[0128]
<< Extraction with Tetrahydrofuran >>
As a control, a concentrated solution of RC-700E (manufactured by Nicca Chemical Co., Ltd.) which serves as the surfactant used in Comparative Example 3 (water dyeing), was diluted about 10000 times with acetonitrile and analyzed by HPLC. The (water dyed) functionalized base material of Comparative Example 3 was further divided into 4 equal pieces having a size of 2 cm x 2 cm (0.0497 g), placed in a vial having a volume of 1.5 ml, and 1.2732 g of THF was added to the vial. The mixture was treated with ultrasonic waves at 40 KHz for 30 minutes at an initial temperature of 25°C, and then allowed to stand one night to obtain a THF extract. The obtained THF extract was diluted about 10- fold with acetonitrile, filtered through a 0.45 pm PTFE filter, and analyzed by HPEC. [0129] <<EC-MS Analysis >>
The THF extract was used as an analytical sample to be subjected to an EC-MS analysis implemented under the following LC-MS conditions and MS conditions.
[0130]
[LC-MS Conditions]
- Mass spectrometer: micrOTOF-QII (manufactured by Bruker Daltonics Inc.)
- UHPLC device: NEXERA XR (manufactured by Shimadzu Corporation)
- Column: YMC-TRIART C18 (manufactured by YMC Co., Ltd., column: 50 x 2.1 mm I.D., particle diameter: 1.9 pm, pore size: 12 nm)
- Column temperature: 40°C - Mobile phase: Phase A: 10 mM aqueous solution of ammonium formate, Phase B: acetonitrile
- Gradient conditions:
- 1 minute to 10 minutes: 60/40 (phase A/phase B, volume ratio)
- 10 minutes to 15 minutes: 2/98 (phase A/phase B, volume ratio) - 15 minutes to 20 minutes: 60/40 (phase A/phase B, volume ratio)
- Volume of injected sample: 10 pL - Ionization method: electrospray ionization (ESI)
- Detected ions: Positive ions
- Source:
- End plate offset: -500 V
- Capillary: 4500 V
- Nebulizer: 2.0 bar
- Drying gas: 8.0 L/min
- Drying temperature: 200°C
- Calibration: Tuning mix ES-TOF (ESI) (manufactured by Agilent Technologies) [0131]
[MS Conditions]
- Mode: Wide
- Funnel 1: 300 Vpp
- Funnel 2: 300 Vpp
- Hexapole: 300 Vpp
- Collision RF: 600 Vpp
- Transfer time: 120 ps
- Pre pulse storage: 8 ps [0132]
For the functionalized base material of Comparative Example 3 and the control surfactant, the three peaks detected in the graphs of the elution time vs. mass were superimposed to obtain spectra to be compared (FIGs. 6 and 7). As a result, a group having the same mass was confirmed, and it was confirmed that the surfactant remained in the functionalized base material of Comparative Example 3.
[0133]
From the above, it was found that a functionalized base material obtained by a dyeing method using water (water dyeing) can be clearly distinguished from the functionalized base material of the present embodiment by examining the content of surfactants by LC-MS analysis or the like, to confirm that the functionalized base material of the present embodiment is substantially free of surfactants.
[0134]
(Example 2)
The functionalizing agent (dye) in Example 1 was changed from Disperse Blue 14 to Disperse Orange 25, and the application step was implemented under the following conditions.
[0135]
The functionalized base material manufacturing apparatus 1 illustrated in FIG. 1 was used to supply 5 mg of Disperse Orange 25 and 15 g of acetonitrile as an entrainer to the high- pressure vessel 6 having a volume of 400 ml at a temperature of 175°C and a pressure of 25 MPa, and Disperse Orange 25 and acetonitrile were dissolved in a supercritical carbon dioxide fluid. The base material was cut to a size of 8 cm x 10 cm, placed on the stage of the conveyance mechanism 14, and heated to a surface temperature of 150°C by the heating mechanism 15. Next, while the base material was being conveyed at a speed of 25 mm/sec, the supercritical carbon dioxide fluid in which Disperse Orange 25was dissolved was discharged in a gas phase state and/or a supercritical state from the pulse valve 10 having the nozzle hole 123 with a diameter of 100 pm, and applied to the polymeric molded body. The polymeric molded body was dyed by maintaining the heated state for 10 minutes, and thus, a functionalized base material of Example 2 was prepared.
[0136]
The functionalized base material obtained in Example 2 was subjected to a washing fastness test based on JIS L 0844 No. A-2. The results indicated grades of 4 and 5 for discoloration after washing and grade 4 for staining after washing. Further, a rubbing fastness test was conducted using a dry test based on the rubbing tester type II method of JIS L 0849. The results were equivalent to grades 3 and 4 for staining after rubbing. These tests were outsourced to the Kaken Test Center, which is a general incorporated foundation.
From these results, it was possible to confirm that the functionalized base material of Example 2 contained a functionalizing agent inside the functionalized base material.
[0137] Embodiments have been described above, however, the present disclosure is not limited to the above-described embodiments, and various modifications and improvements are possible within the scope of the present disclosure.
[0138]
Aspects of the present disclosure include, for example, the following.
In a first aspect, a method of manufacturing a functionalized base material includes: discharging and applying to a base material a supercritical fluid in a gas phase state or a supercritical state in which a functionalizing agent is dissolved.
According to a second aspect, in the method according to the first aspect, the base material comprises a polymeric molded body.
According to a third aspect, in the method according to the first aspect or the second aspect, the functionalizing agent comprises a dye.
According to a fourth aspect, in the method according to any one of the first aspect to the third aspect, the base material is in a form of fabric.
According to a fifth aspect, in the method according to any one of the first aspect to the fourth aspect, the functionalizing agent comprises at least one selected from the group consisting of a preservative, an antifungal agent, a waterproofing agent, and a conductive agent.
According to a sixth aspect, in the method according to any one of the first aspect to the fifth aspect, the functionalizing agent includes a first functionalizing agent and a second functionalizing agent, and the discharging and applying includes: discharging and applying to the base material a supercritical fluid in a gas phase state in which the first functionalizing agent is dissolved, and discharging and applying to the base material a supercritical fluid in a gas phase state in which the second functionalizing agent is dissolved.
In a seventh aspect, a functionalized base material includes: a base material including oligomers where a content of internal oligomers is 50 mass% or more of all the oligomers in the base material; and a functionalizing agent, and the functionalized base material is substantially free of a surfactant.
According to an eighth aspect, in the functionalized base material according to the seventh aspect, the base material comprises a polymeric molded body.
According to a ninth aspect, in the functionalized base material according to the seventh aspect or the eighth aspect, the content of internal oligomers is 0.8 mass% or more of the functionalized base material.
According to a tenth aspect, in the functionalized base material according to any one of the seventh aspect to the ninth aspect, the functionalizing agent is in a form of fabric.
According to an eleventh aspect, in the functionalized base material according to any one of the seventh aspect to the tenth aspect, the functionalizing agent comprises a dye.
According to a twelfth aspect, in the functionalized base material according to the eleventh aspect, a discoloration degree and a staining degree, evaluated by a washing fastness test according to JIS L 0844 No. A-2, are grade 4 or higher and grade3 or higher, respectively, and a staining degree, evaluated by a rubbing fastness test that is a dry test based according to a rubbing tester type II method of JIS L 0849, is grade 3 to 4 or higher.
According to a thirteenth aspect, in the functionalized base material according to any one of the seventh aspect to the twelfth aspect, the functionalizing agent comprises at least one selected from the group consisting of a preservative, an antifungal agent, a waterproofing agent, and a conductive agent.
According to a fourteenth aspect, in the functionalized base material according to any one of the seventh aspect to the thirteenth aspect, a content of the functionalizing agent in a first region of the functionalized base material is different from a content of the functionalizing agent in a second region of the functionalized base material.
According to a fifteenth aspect, in the functionalized base material according to any one of the seventh aspect to the fourteenth aspect, the functionalizing agent includes a first functionalizing agent and a second functionalizing agent.
According to a sixteenth aspect, an apparatus for manufacturing a functionalized base material includes a high-pressure vessel to mix and dissolve a functionalizing agent in a supercritical fluid, and a pulse valve to discharge the supercritical fluid in a gas phase state or a supercritical state in which the functionalizing agent is dissolved, supplied from the high-pressure vessel.
[0139]
The above-described embodiments are illustrative and do not limit the present invention. Thus, numerous additional modifications and variations are possible in light of the above teachings. For example, elements and/or features of different illustrative embodiments may be combined with each other and/or substituted for each other within the scope of the present invention. Any one of the above-described operations may be performed in various other ways, for example, in an order different from the one described above.
[0140]
This patent application is based on and claims priority to Japanese Patent Application No. 2024-096560, filed on June 14, 2024, in the Japan Patent Office, the entire disclosure of which is hereby incorporated by reference herein.
[Reference Signs List]
[0141]
1 Functionalized base material manufacturing apparatus
6 High-pressure vessel
10, 10a Pulse valve
12 Base material

Claims

[CLAIMS]
1. A method of manufacturing a functionalized base material, the method comprising: discharging and applying to a base material a supercritical fluid in a gas phase state or a supercritical state in which a functionalizing agent is dissolved.
2. The method according to claim 1, wherein the base material comprises a polymeric molded body.
3. The method according to claim 1 or 2, wherein the functionalizing agent comprises a dye.
4. The method according to any one of claims 1 to 3, wherein the base material is in a form of fabric.
5. The method according to any one of claims 1 to 4, wherein the functionalizing agent comprises at least one selected from the group consisting of a preservative, an antifungal agent, a waterproofing agent, and a conductive agent.
6. The method according to any one of claims 1 to 5, wherein the functionalizing agent includes a first functionalizing agent and a second functionalizing agent, and the discharging and applying includes: discharging and applying to the base material a supercritical fluid including the first functionalizing agent, in a gas phase state; and discharging and applying to the base material a supercritical fluid including the second functionalizing agent, in a gas phase state.
7. A functionalized base material comprising: a base material including oligomers, a content of internal oligomers being 50 mass% or more of all the oligomers in the base material; and a functionalizing agent, wherein the functionalized base material is substantially free of a surfactant.
8. The functionalized base material according to claim 7, wherein the base material comprises a polymeric molded body.
9. The functionalized base material according to claim 7 or 8, wherein the content of internal oligomers is 0.8 mass% or more of the functionalized base material.
10. The functionalized base material according to any one of claims 7 to 9, wherein the functionalized base material is in a form of fabric.
11. The functionalized base material according to any one of claims 7 to 10, wherein the functionalizing agent comprises a dye.
12. The functionalized base material according to claim 11, wherein a discoloration degree and a staining degree, evaluated by a washing fastness test according to JIS L 0844 No. A-2, are grade 4 or higher and grade3 or higher, respectively, and a staining degree, evaluated by a rubbing fastness test that is a dry test according to a rubbing tester type II method of JIS L 0849, is grade 3 to 4 or higher.
13. The functionalized base material according to any one of claims 7 to 12, wherein a content of the functionalizing agent in a first region of the functionalized base material is different from a content of the functionalizing agent in a second region of the functionalized base material.
14. The functionalized base material according to any one of claims 7 to 13, wherein the functionalizing agent includes a first functionalizing agent and a second functionalizing agent.
15. An apparatus for manufacturing a functionalized base material, the apparatus comprising: a high-pressure vessel to mix a supercritical fluid and a functionalizing agent; and a pulse valve to discharge the supercritical fluid in a gas phase state or a supercritical state in which the functionalizing agent is dissolved, supplied from the high-pressure vessel.
PCT/IB2025/055965 2024-06-14 2025-06-11 Method of manufacturing functionalized base material, functionalized base material, and apparatus for manufacturing functionalized base material Pending WO2025257751A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002004169A (en) * 2000-06-20 2002-01-09 Kenji Mishima Washing, dyeing or functional processing for fiber product and sewed product by high-pressure carbon dioxide utilizing coexisting effect of added auxiliary solvent
JP2007091805A (en) 2005-09-27 2007-04-12 Mitsubishi Materials Corp Processing method of resin molding
US20100075068A1 (en) * 2006-12-01 2010-03-25 Teijin Fibers Limited Method of imparting function to molded polymer and apparatus therefor
JP2024096560A (en) 2023-01-04 2024-07-17 コニカミノルタ株式会社 Document creation method, program for causing a computer to execute said method, and document creation device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002004169A (en) * 2000-06-20 2002-01-09 Kenji Mishima Washing, dyeing or functional processing for fiber product and sewed product by high-pressure carbon dioxide utilizing coexisting effect of added auxiliary solvent
JP2007091805A (en) 2005-09-27 2007-04-12 Mitsubishi Materials Corp Processing method of resin molding
US20100075068A1 (en) * 2006-12-01 2010-03-25 Teijin Fibers Limited Method of imparting function to molded polymer and apparatus therefor
JP2024096560A (en) 2023-01-04 2024-07-17 コニカミノルタ株式会社 Document creation method, program for causing a computer to execute said method, and document creation device

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Title
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