Method for producing functionalized base material, functionalized base material, and apparatus for producing functionalized base material

Abstract

To provide a method for producing a functionalized base material that does not use an agent such as a surfactant, and a large amount of water, reduces contamination on fiber surfaces and deposition in apparatuses by elution of oligomers, is capable of having a functionalization agent adsorbed in an inner part of the base material, or evenly attached on a surface to diffuse in the inner part of the base material, and makes dying in different colors and image formation by a plural kinds of functionalization agents possible by controlling an application amount of the functionalization agent for every application part in a continuous process.SOLUTION: A method for producing a fuctionalized base material having a base material, and a functionalization agent includes: a process of discharging a supercritical fluid dissolved with the functionalization agent in a gas phase state and / or a supercritical state to apply on to the base material.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a method for producing a functionalized substrate, a functionalized substrate, and an apparatus for producing a functionalized substrate. [Background technology]

[0002] Conventional water-based dyeing of fabrics requires the use of chemicals such as solvents and surfactants, generates large amounts of waste liquid for disposal, and requires a large amount of energy for drying, resulting in a very high environmental impact. In response to this problem, dyeing using supercritical carbon dioxide is being considered.

[0003] To date, a batch-type anhydrous dyeing method has been reported in which a resin molding processing method is characterized by contacting a resin molding containing additives with a supercritical fluid in which either a colorant or a functional agent, or both, are dissolved, thereby extracting the additives from the resin molding and applying either a colorant or a functional agent, or both, to the surface layer of the resin molding (see, for example, Patent Document 1).

[0004] Furthermore, a method for imparting functionality to a polymer molded product has been reported for a continuous anhydrous dyeing method, which is characterized by spraying a supercritical fluid onto the polymer molded product and fixing a functionality-imparting agent to the polymer molded product (see, for example, Patent Document 2). Summary of the Invention [Problem to be solved by the invention]

[0005] An object of one embodiment of the present invention is to provide a method for producing a functionalized substrate that does not use chemicals such as surfactants or large amounts of water, reduces fiber surface contamination due to elution of oligomers and deposition within the device, allows a function-imparting agent to be adsorbed inside the substrate or uniformly attached to the surface and diffused into the substrate, and is capable of controlling the amount of function-imparting agent applied to each discharge site in a continuous process, thereby enabling different dyeing and image formation using multiple types of function-imparting agents. [Means for solving the problem]

[0006] A method for producing a functionalized substrate according to one embodiment of the present invention is a method for producing a functionalized substrate having a substrate and a function-imparting agent, and includes a step of discharging and applying a supercritical fluid containing the function-imparting agent to the substrate in a gaseous state or a supercritical state. [Effects of the Invention]

[0007] According to one embodiment of the present invention, a method for producing a functionalized substrate can be provided that does not use chemicals such as surfactants or large amounts of water, reduces fiber surface contamination due to elution of oligomers and deposition within the apparatus, allows a function-imparting agent to be adsorbed inside the substrate or uniformly attached to the surface and diffused into the substrate, and is a continuous process that allows the amount of function-imparting agent to be controlled for each application site, making it possible to perform different dyeing and image formation using multiple types of function-imparting agents. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram showing an example of a manufacturing apparatus for a functionalized substrate according to this embodiment. [Figure 2] FIG. 2 is a cross-sectional view showing an example of a pulse valve in the apparatus for producing a functionalized substrate according to this embodiment. [Figure 3] FIG. 3 is a partial cross-sectional view showing an example of the configuration of the pulse valve of FIG. [Figure 4] FIG. 2 is a cross-sectional view showing another example of a pulse valve in the apparatus for producing a functionalized substrate according to this embodiment. [Figure 5] FIG. 5 is a cross-sectional view of the pulse valve of FIG. 4 taken along line AA. [Figure 6] FIG. 6 shows a spectrum derived from the surfactant in the functionalized substrate of Comparative Example 3. [Figure 7] FIG. 7 shows the spectra of surfactants. DETAILED DESCRIPTION OF THE INVENTION

[0009] (Method of manufacturing functionalized substrate) The method for producing a functionalized substrate of this embodiment is a method for producing a functionalized substrate having a substrate and a function-imparting agent, and includes a step (application step) of applying a supercritical fluid containing the function-imparting agent to the substrate by ejecting it in a gaseous state or a supercritical state, and further includes other steps as necessary. The method for producing a functionalized substrate can be suitably carried out by a manufacturing apparatus for a functionalized substrate according to this embodiment, which will be described later.

[0010] The present invention is based on the inventors' discovery of the following problems in the prior art. In other words, in the conventional batch-type anhydrous dyeing method, oligomers contained in the fiber are eluted onto the fiber surface and accumulate in the batch, and in addition, they reattach to the fiber, hindering even dyeing. The size of the fiber or fabric is limited to the size that can be stored in the batch container, and it was necessary to cut the fabric for each batch and dye the entire fiber or fabric together in batches. Furthermore, in the continuous anhydrous dyeing method described in Patent Document 2, a reactor having a gap that is approximately inverted T-shaped in cross section is used, and a functional material liquid and supercritical carbon dioxide mixed in a mixing coil are sprayed onto a polymer molded product such as a fiber that is running through the gap. However, since the functional material that cannot be completely dissolved in the supercritical carbon dioxide is sprayed as a liquid, there is a problem in that it is difficult to apply the functional material uniformly to the fiber, to apply it locally, and to control the amount of application.

[0011] As a result of intensive research to achieve the above object, the present inventors have found that, by including a step of applying a supercritical fluid containing the function-imparting agent to the substrate by discharging it in a gaseous phase and / or a supercritical state, it is possible to reduce fiber surface contamination due to elution of oligomers and deposition inside the device without using chemicals such as surfactants or large amounts of water, to adsorb the function-imparting agent inside the substrate or to uniformly adhere it to the surface and diffuse it into the substrate, and to control the amount of the function-imparting agent applied to each application site in a continuous process, thereby enabling different dyeing and image formation using multiple types of function-imparting agents, and have completed the present invention.

[0012] <Application process> The applying step is a step of applying a supercritical fluid containing the functionalizing agent to the base material by ejecting the supercritical fluid in a gaseous state or a supercritical state. The application step can be suitably carried out by using a high-pressure vessel and a pulse valve in a manufacturing apparatus for a functionalized substrate of this embodiment, which will be described later. The ejected supercritical fluid does not contain a liquid phase.

[0013] To apply the supercritical fluid containing the functionalizing agent to the substrate by ejecting it in a gaseous or supercritical state, the temperature and pressure of a high-pressure container are controlled so that the supercritical fluid or a mixture of the supercritical fluid and an entrainer does not change from the supercritical state to a liquid or solid state when the supercritical fluid containing the functionalizing agent is ejected from the nozzle (i.e., when the fluid expands), and the supercritical fluid is sprayed onto the polymer structure from the nozzle. For example, if the supercritical fluid is supercritical carbon dioxide fluid without an entrainer, the supercritical fluid can be ejected and applied in a gaseous or supercritical state by controlling the high-pressure container to 390 K (about 117°C) or higher at 25 MPa and 408 K (about 135°C) or higher at 40 MPa, referring to the Mollier diagram for carbon dioxide alone.

[0014] The application step enables continuous process discharge by transporting the substrate to be applied or scanning the discharge position of a pulse valve or the like relative to the substrate, and also enables control of the amount of function-imparting agent applied to each application region of the substrate, thereby enabling application of the function-imparting agent to specific regions of the substrate, different dyeing, and image formation. Specific examples of such embodiments include an embodiment in which the content of the function-imparting agent in a first region of the functionalized substrate is different from the content of the function-imparting agent in a second region of the functionalized substrate.

[0015] Furthermore, the imparting step may include a first imparting step and a second imparting step. Specifically, a preferred embodiment of the method for producing a functionalized substrate includes a first imparting step in which the function-imparting agent has a first function-imparting agent and a second function-imparting agent, and the first imparting step includes a first imparting step in which a supercritical fluid having the first function-imparting agent dissolved therein is discharged onto the substrate in a gaseous state and / or a supercritical state to impart the first function-imparting agent to the substrate, and a second imparting step in which a supercritical fluid having the second function-imparting agent dissolved therein is discharged onto the substrate in a gaseous state and / or a supercritical state to impart the second function-imparting agent to the substrate. There are no particular limitations on the first function-imparting agent and the second function-imparting agent, and different function-imparting agents can be selected depending on the purpose. This embodiment makes it possible to dye differently or form images using a plurality of types of function-imparting agents.

[0016] -Base material- The substrate is not particularly limited and can be appropriately selected depending on the purpose, but is preferably a polymer molded article made of a polymer. The material for the polymer molded body is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyester-based polymers such as polyethylene terephthalate (PET); polyolefin-based polymers; polyamide-based polymers such as nylon 6; acrylic-based polymers such as polyacrylonitrile; acetate-based polymers; polyvinyl chloride-based polymers; and aramid-based polymers. The shape of the polymer molded product may be a fiber such as a raw yarn or twisted yarn, a cloth such as a woven fabric, a knitted fabric or a nonwoven fabric, or a film or plate, and any of these may be suitably applied. Among these, the cloth, film or plate shape is preferred, and the cloth shape is more preferred, in that it allows for the advantage of enabling separate dyeing and image formation.

[0017] The polyester polymer is preferably polyethylene terephthalate. The polyethylene terephthalate may have a copolymerization component, and preferably has 90 mol % or more of polyethylene terephthalate repeating units, and more preferably has 95 mol % or more of polyethylene terephthalate repeating units. The polymer molded article may contain any copolymer 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 of above its critical temperature and above its critical pressure. For example, a supercritical carbon dioxide fluid refers to a carbon dioxide fluid under supercritical conditions of above its critical temperature of 31.1°C and above its critical pressure of 7.48 MPa.

[0019] The supercritical fluid can also be used in conjunction with an entrainer (co-solvent). Examples of the entrainer include 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 may be used alone or in combination of two or more.

[0020] -Functionalizing agent- The function-imparting agent is not particularly limited and can be appropriately selected depending on the purpose and the physicochemical properties of the substrate, and examples thereof include dyes, antiseptics, antifungal agents, waterproofing agents, conductive agents, ultraviolet absorbers, strength-increasing agents, oxidizing agents, neutralizing agents, metal or catalyst deactivators, slip agents, light stabilizers, anti-blocking agents, lubricants, fire retardants, coupling agents, processing aids, antistatic agents, nucleating agents, foaming agents, etc. Among these, dyes are preferred when used for dyeing purposes, and antiseptics, antifungal agents, waterproofing agents, and conductive materials are preferred when used for various other purposes. These may be used alone or in combination of two or more. Specifically, two or more may be mixed and applied in one application step, or two or more may be applied individually in two or more application steps.

[0021] The function-imparting agent is preferably selected so that it does not elute from the functionalized substrate under actual use conditions, and does not substantially dissolve in the functionalized substrate or substrate under normal conditions, or dissolves in only a very small amount, if at all.

[0022] Examples of the dyes include disperse dyes, acid dyes, acid mordant dyes, basic dyes, direct dyes, construction dyes, reactive dyes, and naphthol dyes. Among these, disperse dyes are preferred because of their excellent solubility in supercritical carbon dioxide fluid. When performing aqueous dyeing using a disperse dye, a dispersant is added to the disperse dye to stably disperse the disperse dye in water, but in the method for producing a functionalized substrate of this embodiment, the disperse dye can be used by mixing it with a supercritical fluid without using a dispersant.

[0023] Examples of disperse dyes include 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 may be used alone or in combination of two or more.

[0024] Examples of the preservatives and antifungal agents include Marcuside YP-DP (manufactured by Osaka Chemical Industry Co., Ltd.), Amorden HS (manufactured by Yamato Chemical Industry Co., Ltd.), catechin, chitosan, flavone, acrylonitrile, and polyanions having multiple anionic functional groups, such as carboxyl groups, sulfonic acid groups, sulfate groups, or phosphate groups, per molecule. Examples of the waterproofing agent include 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 agent include silver acetylacetonate, dimethylcyclooctadiene platinum II, and bisacetylacetonate palladium. Examples of the fire retardant include aromatic condensed phosphate esters.

[0025] Examples of ultraviolet absorbers include benzotriazoles and benzophenones. Examples of the strength enhancer include silicone oil. Examples of the neutralizing agent or catalyst deactivator include zinc oxide, zinc stearate, aliphatic amines, and aliphatic amides. Examples of metals include copper, silver, nickel, and gold. Examples of slip agents include erucamide, oleamide, and ethylene bisstearamide. Examples of light stabilizers include benzophenones. Examples of anti-blocking agents include diatomaceous earth silica, clay, and talc. Examples of lubricants include organically modified polydimethylsiloxane, etc. Examples of processing aids include calcium stearate, organically modified polydimethylsiloxane, etc. Examples of antistatic agents include glycerol monostearate, ethoxylated amines, polyethylene glycol esters, and quaternary ammonium compounds. Examples of the foaming agent include azodicarbonamide and sodium bicarbonate.

[0026] (Functionalized base material) The functionalized substrate of this embodiment is a functionalized substrate having a substrate and a function-imparting agent. The functionalized substrate is substantially free of surfactants, and the content of internal oligomers relative to all oligomers in the substrate is 50% by mass or more.

[0027] <Base material> The substrate is not particularly limited and can be selected appropriately depending on the purpose from the items described above regarding the substrate in the method for producing a functionalized substrate of this embodiment. The shape of the substrate and the functionalized substrate is not particularly limited and can be appropriately selected depending on the purpose, but is preferably cloth-like.

[0028] <Functionalizing agents> The function-imparting agent is not particularly limited and can be appropriately selected depending on the purpose from the items described above regarding the function-imparting agent in the method for producing a functionalized substrate of this embodiment. The function-imparting agent is not particularly limited and can be appropriately selected depending on the purpose. In one embodiment, the function-imparting agent is preferably a dye. In another or additional embodiment, the function-imparting agent is preferably one or more selected from the group consisting of an antiseptic, an antifungal agent, a waterproofing agent, and a conductive agent.

[0029] The functionalized substrate of this embodiment enables the application of a function-imparting agent to specific portions of the substrate, and enables dyeing and image formation. Specific examples of such embodiments include an embodiment in which the content of the function-imparting agent in a first region of the functionalized substrate is different from the content of the function-imparting agent in a second region of the functionalized substrate.

[0030] Also suitable is an embodiment in which the function-imparting agent includes a plurality of function-imparting agents, for example, an embodiment having a first function-imparting agent and a second function-imparting agent. In this case, by mixing and applying the first function-imparting agent and the second function-imparting agent, the first function-imparting agent and the second function-imparting agent may be present in specific regions of the functionalized substrate. By performing the first and second applying steps, the functionalized substrate may have different contents and application patterns of the first function-imparting agent and different contents and application patterns of the second function-imparting agent in different regions of the functionalized substrate. Either embodiment can be appropriately selected depending on the purpose.

[0031] <Oligomer> The content of internal oligomers relative to all oligomers in the functionalized substrate is 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more. The content of surface oligomers relative to all oligomers in the functionalized substrate is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0032] As mentioned above, conventional batch-type anhydrous dyeing methods have the problem that oligomers contained in fibers dissolve onto the fiber surface and accumulate in the batch, and also redeposit on the fibers, hindering dye leveling. Therefore, compared with fibers before dyeing, fibers dyed with a batch-type anhydrous dyeing method have a reduced amount of internal oligomers (e.g., less than 50% of the total oligomers) and an increased amount of surface oligomers (e.g., more than 50% of the total oligomers).

[0033] In contrast, according to the method for producing a functionalized substrate and the functionalized substrate of the present embodiment, a supercritical fluid in which a function-imparting agent is dissolved is applied to the substrate by being discharged in a gaseous and / or supercritical state, rather than holding the substrate in a heated state in a batch for a long period of time as in a batch-type anhydrous dyeing method, making it possible to control the amount of application locally and reduce the time the substrate is exposed to an atmosphere that is prone to elution of oligomers. Therefore, according to the present embodiment, application is performed under reduced pressure, which shortens the processing time, makes it difficult for oligomers to elute from inside the substrate, prevents oligomers from remaining in the batch, reduces the loss of internal oligomers in the functionalized substrate, and reduces the elution of surface oligomers.

[0034] It has been reported that polyester fibers before dyeing generally contain approximately 1% by mass of oligomers in total, and that the surface oligomers adhering to the surface of polyester fibers are approximately 0.1% by mass (Development of polyester oligomer remover: Atsushi Kamiya, Yasunari Sawanoi, Hiroyuki Hasebe). As will be apparent from the examples described below, the total oligomer content was approximately 1.4% by mass, and the surface oligomer content was 0.11% by mass, which is consistent with the previous report (see Comparative Example 1 in Table 1). From the above, by confirming the oligomer content and distribution (and the presence or absence of surfactants) in the functionalized substrate, it is possible to distinguish dyed products obtained by conventional batch-type anhydrous dyeing (and water dyeing) from the functionalized substrate of this embodiment.

[0035] The content of internal oligomers in the functionalized substrate is preferably 0.8% by mass or more, more preferably 0.9% by mass or more, and even more preferably 1.0% by mass or more, relative to the total amount of the functionalized substrate, from the viewpoint of reducing oligomer elution from the substrate. The content of internal oligomers in the functionalized substrate can be appropriately selected depending on the oligomer content of the substrate used, and is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, relative to the total oligomer content of the substrate. The content of surface oligomers in the functionalized substrate is preferably 0.7% by mass or less, more preferably 0.6% by mass or less, and even more preferably 0.5% by mass or less, relative to the total amount of the functionalized substrate.

[0036] The total oligomer content in the functionalized substrate can be determined by a known method appropriately selected depending on the type of substrate used. For example, the substrate is completely dissolved in a solvent capable of dissolving the substrate, and then a polymer is precipitated using an appropriate solvent. The precipitated polymer is removed by filtration, whereby all oligomers can be extracted and quantitatively analyzed. Specifically, when the substrate is polyethylene terephthalate (PET), the functionalized substrate is completely dissolved in hexafluoropropanol, the polymer is precipitated with acetonitrile, and then filtered. The hexafluoropropanol extract obtained is then subjected to HPLC analysis and quantification of the oligomers.

[0037] -Hexafluoropropanol extraction- Specifically, the analytical sample for total oligomer analysis can be obtained by the following procedure. A 1 cm x 1 cm piece of the functionalized substrate is cut into an evaluation sample. This evaluation sample is divided into four equal parts, one of which is placed in a 10 ml vial and approximately 0.6 ml of hexafluoropropanol is added. After leaving it for about two hours, approximately 9.4 ml of acetonitrile is added and the mixture is filtered through a PTFE filter with a pore size of 0.2 μm to obtain the analytical sample for total oligomer analysis.

[0038] The content of surface oligomers in the functionalized substrate can be determined by appropriately selecting a known method depending on the type of substrate used. For example, the surface oligomers can be extracted and quantitatively analyzed by dissolving the surface of the substrate in a solvent capable of dissolving the surface of the substrate. Specifically, when the substrate is polyethylene terephthalate (PET), the content of internal oligomers can be measured by extracting the functionalized substrate with tetrahydrofuran, analyzing it by HPLC, and quantifying the oligomers. The content of internal oligomers can be calculated as the difference between the content of total oligomers and the content of surface oligomers.

[0039] -Tetrahydrofuran extraction- Specifically, the analytical sample for surface oligomer analysis can be obtained by the following procedure. A portion (approximately 0.015 g) of the functionalized substrate is taken as an evaluation sample and placed in a 10 ml vial, followed by approximately 5 ml of THF. Ultrasonic treatment is performed at an initial temperature of 25°C and 40 kHz for 30 minutes, and the mixture is left overnight to obtain a THF extract. Approximately 9.5 ml of acetonitrile is added to 1 ml of the THF extract to obtain the analytical sample for surface oligomer analysis.

[0040] -HPLC analysis- HPLC analysis can be performed using an analytical sample for total oligomer analysis or an analytical sample for surface oligomer analysis under the following HPLC conditions.

[0041] [HPLC conditions] HPLC equipment: ACQUITY UPLC H-Class system (Waters) Column: ACQUITY UPLC BEH C18 (Waters, Column: 50 x 2.1 mm l.D., Particle size: 1.7 μm) Column temperature: 40℃ Mobile phase: Phase A: 10 mM ammonium formate aqueous solution, Phase B: acetonitrile Gradient conditions: 0 to 5 minutes: 99 / 1 (A phase / B phase, volume ratio) 5 minutes to 6.25 minutes: 1 / 99 (A phase / B phase, volume ratio) 6.25 minutes to 7.5 minutes: 1 / 99 (A phase / B phase, volume ratio) 7.5 minutes and above: 99 / 1 (A phase / B phase, volume ratio) Sample injection volume: 5 μL Sample temperature: 10℃ UV conditions: Capture wavelength: 195nm-480nm, Resolution: 1.2nm

[0042] -Quantitative analysis of oligomers- Regarding the method for calculating quantitative values ​​from HPLC peak areas, when the base material is polyethylene terephthalate (PET), the quantitative value of the oligomer to be measured, cyclic trimer of dimethyl phthalate (CDMP) can be calculated from the quantitative value of dimethyl phthalate (DMP).

[0043] Specifically, a calibration curve for dimethyl phthalate is calculated from the measurement results of a DMP standard solution. Approximately 60 mg of dimethyl phthalate is dissolved and diluted with acetonitrile in a 50 ml measuring flask to prepare a DMP standard solution with a known concentration of 1200 ppm, which is then serially diluted for use. The DMP content is calculated from the HPLC peak area corresponding to the oligomer, and then the DMP content is converted to the CDMP content, assuming that the molar absorption coefficient of CDMP is three times that of DMP.

[0044] <Surfactant> The functionalized substrate is substantially free of surfactants. Here, "substantially free" means that when the functionalized substrate is extracted with tetrahydrofuran (THF) and subjected to component analysis, the amount of the surfactant to be evaluated is below the detection limit.

[0045] Here, conventional dyeing using water uses water containing dye, dispersant, etc. in the dyeing process, and also uses a large amount of water containing surfactant, reducing agent, etc. in the washing process, resulting in the disposal of a large amount of waste liquid and the need for a large amount of energy for drying, resulting in a very high environmental load. According to the method for producing a functionalized substrate and the functionalized substrate of this embodiment, a large amount of dye does not adhere to the surface of a substrate such as a fiber, so there is no need for soaping using a surfactant, etc., and no additives such as a dispersant are required. Therefore, not only do not chemicals such as surfactants or large amounts of water need to be used, but the functionalized substrate has the characteristic of being substantially free of surfactants.

[0046] Specifically, the THF extract of the functionalized substrate and the sample for component analysis can be obtained by the following procedure. A portion of the functionalized substrate (approximately 0.01 g) is taken as an evaluation sample and placed in a 1.5 ml vial, and approximately 1.2 g of THF is added. Ultrasonication is performed at an initial temperature of 25°C and 40 kHz for 30 minutes, and the mixture is left overnight to obtain a THF extract. The obtained THF extract is diluted approximately 10-fold with acetonitrile and filtered through a 0.45 μm PTFE filter to obtain a sample for component analysis.

[0047] The component analysis of the THF extract of the functionalized substrate and the fact that it is substantially free of surfactants can be confirmed by, specifically, performing LC-MS analysis under the following LC-MS and MS conditions, and finding that no peak for the target surfactant is detected.

[0048] [LC-MS conditions] ·Mass spectrometer: micrOTOF-QII (manufactured by Bruker Daltonics) UHPLC equipment: Nexera XR (Shimadzu Corporation) Column: YMC-Triart C18 (YMC Corporation, column: 50 x 2.1 mm l.D., particle size: 1.9 μm, pore size: 12 nm) Column temperature: 40℃ Mobile phase: Phase A: 10 mM ammonium formate aqueous solution, Phase B: acetonitrile Gradient conditions: 1 minute to 10 minutes: 60 / 40 (phase A / phase B, volume ratio) 10-15 minutes: 2 / 98 (phase A / phase B, volume ratio) 15-20 minutes: 60 / 40 (phase A / phase B, volume ratio) Sample injection volume: 10 μL Ionization method: Electrospray ionization (ESI) Detected ions: positive ions ·sauce: End plate offset: -500V Capillary: 4500V Nebulizer: 2.0 bar Drying gas: 8.0L / min ·Drying temperature: 200℃ Calibration: Tuning mix ES-TOF (ESI) (Agilent Technologies)

[0049] [MS conditions] Mode: Wide Funnel 1: 300Vpp Funnel 2: 300Vpp Hexapole: 300Vpp Collision RF: 600Vpp Transfer time: 120μs Pre plus storage: 8μs

[0050] The functionalized substrate preferably contains the function-imparting agent inside the functionalized substrate. Here, "containing the function-imparting agent inside" can be confirmed, for example, by evaluating wash fastness or friction fastness, that the function-imparting agent, such as a dye, does not elute or fall off from the functionalized substrate. Specifically, this can be evaluated by satisfying at least one of the following (1) to (3), and it is preferable to evaluate that all of the following (1) to (3) are satisfied: (1) Washing fastness based on JIS L 0844 A-2 is grade 4 or higher (2) Washing fastness staining grade 3 or higher based on JIS L 0844 A-2 (3) Friction fastness to soiling in a dry test based on the JIS L 0849 friction tester type II method (Gakushin type method) is 3-4 grade or higher.

[0051] Furthermore, 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, so evaluations can be made in accordance with the respective corresponding standards.

[0052] Methods for evaluating the presence of a function-imparting agent other than a dye inside a functionalized substrate include, for example, a method for comparing the content of the function-imparting agent in a functionalized substrate after a washing test for the washing fastness test with the content of the function-imparting agent in a control functionalized substrate that has not been subjected to a washing test; and a method for comparing the content of the function-imparting agent in a functionalized substrate after a friction test for the friction fastness test with the content of the function-imparting agent in a control functionalized substrate that has not been subjected to a friction test. The method for quantifying the content of the function-imparting agent can be appropriately selected depending on the type of function-imparting agent used. The ratio of the content of the function-imparting agent (C1) in the functionalized substrate after a washing test or a friction test to the content of the function-imparting agent (C0) in the control functionalized substrate: (C1 / C0) × 100 (mass%) is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more.

[0053] (Functionalized substrate manufacturing equipment) The manufacturing apparatus for a functionalized substrate of this embodiment includes a high-pressure vessel for mixing a supercritical fluid and a function-imparting agent, and a pulse valve for discharging the supercritical fluid in which the function-imparting agent is dissolved, supplied from the high-pressure vessel, in a gaseous state and / or a supercritical state, and may further include other components as necessary. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following describes the preferred embodiments of the present invention with reference to the accompanying drawings. In the drawings, the same components are designated by the same reference numerals, and redundant explanations may be omitted.

[0054] Referring to FIG. 1, a functionalized substrate manufacturing apparatus 1 according to this embodiment will be described. 1 is a schematic diagram showing an example of a manufacturing apparatus for a functionalized substrate according to this embodiment. The manufacturing apparatus for a functionalized substrate 1 includes a generation unit 30 that generates a supercritical fluid, a supply unit 40 that supplies a function-imparting agent, a high-pressure vessel 6 that mixes the supercritical fluid generated in the generation unit 30 with the function-imparting agent supplied from the supply unit 40 to obtain a mixture of the two, a pulse valve 10 that discharges the mixture supplied from the high-pressure vessel 6 onto a substrate 12, and a pipe 51 that connects the high-pressure vessel 6 and the pulse valve 10. The mixture of the supercritical fluid and the function-imparting agent may also be simply referred to as a "mixture."

[0055] As shown in FIG. 1, the generation unit 30 includes a cylinder 3 for storing liquid carbon dioxide, a cooler 31 for cooling the liquid carbon dioxide supplied from the cylinder 3 via a high-pressure valve 101 to below its saturation temperature, a high-pressure pump 32 for pressurizing the liquid carbon dioxide to a predetermined pressure, a heater 33 for heating the liquid carbon dioxide supplied from the high-pressure pump 32 to a predetermined temperature, and a back-pressure valve 102 for returning excess 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 is a chiller device that circulates cooling water to cool an object to be cooled. An example of the high-pressure pump 32 is a double plunger pump that can control the amount of liquid discharged and prevent pulsation. However, the cooler 31 and the high-pressure pump 32 are not limited to these.

[0057] Liquid carbon dioxide pressurized by a high-pressure pump 32 is heated by a heater 33 to vaporize the carbon dioxide, which is then introduced into a high-pressure vessel 6 and heated and pressurized to bring the carbon dioxide into a supercritical state.

[0058] As shown in FIG. 1, the supply unit 40 includes a container 4 for storing a function-imparting agent and, if necessary, an entrainer, a high-pressure pump 41 for pressurizing the function-imparting agent supplied from the container 4 via a high-pressure valve 106 to a predetermined pressure, and a heater 42 for heating the function-imparting agent supplied from the high-pressure pump 41 to a predetermined temperature.

[0059] The high-pressure vessel 6 mixes, under a high-pressure environment, the supercritical fluid supplied from the generation unit 30 via the high-pressure valve 103 and the function-imparting agent supplied from the supply unit 40 via the high-pressure valve 107. An example of the high-pressure vessel 6 is, but is not limited to, an autoclave.

[0060] The high-pressure vessel 6 has a vessel body 21 that contains a supercritical fluid and a function-imparting agent, a stirring mechanism 22 that stirs the supercritical fluid and the function-imparting agent introduced into the vessel 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 of a motor), a single screw, a twin-shaft screw that intermeshes with each other, a twin-shaft mixer with multiple intermeshing or overlapping stirring elements, a kneader with intermeshing spiral stirring elements, a static mixer, etc. Preferably, the high-pressure vessel 6 further includes a heater 8 for heating the vessel.

[0062] In the initial stage of mixing the supercritical fluid and the function-imparting agent in the high-pressure vessel 6, the supercritical fluid and the function-imparting 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. In contrast, as the mixing of the supercritical fluid and the function-imparting agent progresses, the viscosity of the mixture decreases. Accordingly, the torque of the stirring mechanism 22 also decreases. Furthermore, as the supercritical fluid and the function-imparting agent are sufficiently mixed, the viscosity of the mixture further decreases, and then the decrease in viscosity stops. Accordingly, the torque of the stirring mechanism 22 also becomes constant. In other words, by detecting that the torque of the stirring mechanism 22 has become constant, the torque meter 23 can determine that the supercritical fluid and the function-imparting agent are sufficiently mixed.

[0063] In the high-pressure vessel 6, the supercritical carbon dioxide fluid and the function-imparting agent are mixed under high pressure, for example, about 40 MPa to 50 MPa. Therefore, it is generally not possible to visually observe the progress of mixing of the supercritical carbon dioxide fluid and the function-imparting agent by, for example, opening the lid of the high-pressure vessel 6. In contrast, by using the torque meter 23 to measure the transition in torque of the stirring mechanism 22, it is possible to determine whether the supercritical carbon dioxide fluid and the function-imparting agent are uniformly mixed without visually observing the inside of the high-pressure vessel 6. As a result, unmixed function-imparting agent is prevented 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 the control device 24. Furthermore, the control device 24 may determine whether the supercritical fluid and the function-imparting agent are uniformly mixed based on the torque measurement signal of the torque meter 23. Furthermore, the control device 24 may control the opening and closing of the high-pressure valve 104 disposed downstream of the high-pressure vessel 6 based on the determination result.

[0065] High-pressure valves 104 and 105 are provided downstream of the flow path of the high-pressure vessel 6. The high-pressure valve 104 is provided in the upper part of the high-pressure vessel 6, and by adjusting the supercritical state of the high-pressure vessel 6, it is possible to selectively extract only the gas phase from the high-pressure valve 104 even in a gas-liquid equilibrium state. In addition, the high-pressure valve 105 is provided in the lower part of the high-pressure vessel 6, and it is possible to extract the liquid phase from the high-pressure valve 105, or to send the waste liquid containing the function-imparting agent to the waste liquid tank 9 through the pipe 52.

[0066] When the high-pressure valve 104 is opened, the mixture in the high-pressure vessel 6 is supplied to the pulse valve 10 through the pipe 51. It is also preferable to provide a heating mechanism or a heat insulating member around the pipe 51. This makes it possible to maintain the pipe 51 at a predetermined temperature, and as a result, it is possible to transport and discharge the supercritical fluid in which the functionalizing agent is dissolved in a gaseous state and / or a supercritical state while maintaining the supercritical state of the carbon dioxide flowing through the pipe 51.

[0067] The pulse valve 10 is connected to the tip of the pipe 51. This allows the pulse valve 10 to communicate with the pipe 51, and the mixture that has flowed through the pipe 51 is introduced into the pulse valve 10. The pulse valve 10 then discharges the introduced mixture onto the substrate 12 in a gaseous state and / or a supercritical state.

[0068] The substrate 12 is placed on a transport mechanism 14, and the position of the substrate 12 relative to the pulse valve 10 can be controlled by the transport mechanism 14, such as a stage. The transport mechanism 14 may further or separately include a heating mechanism 15. The heating mechanism 15 heats the substrate 12 to a predetermined temperature. Examples of the heating mechanism 15 include a heater, a hot air generator, and a laser for local heating. With this configuration, the amount of function-imparting agent to be applied to each application region of the substrate 12 can be controlled by adjusting the discharge rate and transport speed, making it possible to apply the function-imparting agent to specific regions of the substrate, and to perform different dyeing or image formation.

[0069] A mixture having a temperature exceeding 150°C (e.g., 170°C) and a pressure of approximately 40 MPa to 50 MPa is introduced into the pulse valve 10. The pulse valve 10 discharges the mixture in a gaseous state and / or a supercritical state toward the substrate 12 while maintaining the temperature and pressure of the mixture at the time of introduction. The pulse valve 10 also performs high-speed opening and closing operations so that the opening time is, for example, 100 μsec or less. This allows the pulse valve 10 to stably discharge a desired amount of mixture. Details of the pulse valve 10 will be described later in the section <Configuration of the Pulse Valve>.

[0070] [Operation of functionalized substrate manufacturing apparatus 1] 1, the operation of discharging a mixture in the functionalized substrate manufacturing apparatus 1 will be described. First, liquid carbon dioxide stored in a cylinder 3 is passed through a high-pressure valve 101 and cooled in a cooler 3 to a temperature below its saturation temperature.

[0071] Subsequently, the supercritical carbon dioxide fluid that has passed through the cooler 31 is introduced into the suction part of the high-pressure pump 32. The liquid carbon dioxide introduced into the high-pressure pump 32 from the suction part is pressurized to a predetermined pressure (for example, 7.3 MPa, which is the critical pressure of carbon dioxide) or higher inside the high-pressure pump 32. During constant-pressure operation, the liquid carbon dioxide introduced into the high-pressure pump 32 is returned to the suction part of the high-pressure pump 32 by the back-pressure valve 102.

[0072] Next, the pressurized liquid carbon dioxide is heated to a predetermined temperature (for example, 31° C., which is the critical temperature of carbon dioxide) or higher by the heater 33. As a result, supercritical carbon dioxide is produced from the liquid carbon dioxide.

[0073] Next, the generated supercritical carbon dioxide fluid is introduced via a high-pressure valve 103 into a high-pressure vessel 6 that has been heated to a predetermined temperature by a heater 8. The supercritical carbon dioxide fluid is melted and mixed with a function-imparting agent that has been introduced into the high-pressure vessel 6 via a separate route by a stirring mechanism 22 connected to a motor 7.

[0074] At this time, the mixture is heated to, for example, about 170° C. by the heater 8. The mixture is also pressurized to, for example, a pressure of about 40 MPa to 50 MPa by a predetermined pressure-increasing mechanism.

[0075] In this embodiment, a mixture of supercritical carbon dioxide and a function-imparting agent is obtained through these mixing processes. Whether a uniform mixture has been obtained can be determined based on the measurement value of the torque meter 23 that measures the torque of the stirring mechanism 22.

[0076] Next, the high-pressure valve 104 is opened. As a result, the mixture in the high-pressure vessel 6 flows through the pipe 51 toward the pulse valve 10. The pulse valve 10 maintains the temperature and pressure of the mixture introduced therein, and repeatedly opens and closes the valves provided therein, thereby discharging a desired amount of the mixture onto the substrate 12.

[0077] <Pulse valve configuration> Next, the configuration of the pulse valve 10 of the functionalized substrate manufacturing apparatus 1 will be described with reference to Figures 2 and 3. Figures 2 and 3 are vertical cross-sectional views of the pulse valve 10.

[0078] 2, the pulse valve 10 has a housing portion 110 having a flow path 112 for a fluid to be discharged therein, a nozzle portion 120 attached to the tip side of the housing portion 110 and discharging the fluid to be discharged, a needle 130 inserted into the housing portion 110 and opening and closing the flow path 112 of the housing portion 110, a drive mechanism 140 for moving the needle 130 back and forth, and a heat-insulating flange 150 provided between the housing portion 110 and the drive mechanism 140. The fluid to be discharged in this embodiment is a mixture of a supercritical fluid and a function-imparting agent.

[0079] Here, the illustrated X direction corresponds to the front-to-rear direction of the pulse valve 10. The Y direction corresponds to the width direction of the pulse valve 10. The Z direction corresponds to the height direction of the pulse valve 10.

[0080] <<Housing section>> The housing part 110 is located at the front of the pulse valve 10 and is a case that accommodates the mixture introduced from the pipe 441. The tip surface of the housing part 110 (the frontmost surface on the +X direction side) faces the substrate 12.

[0081] The housing 110 has a base 111. Inside the base 111, a flow path 112 for the mixture, which is the object to be discharged, is formed. In this embodiment, the flow path 112 is formed along the X direction. Furthermore, a first hole 113 recessed toward the flow path 112 is formed in the upper surface (the uppermost surface on the +Z direction side) of the base 111. A 1 / 8-inch pipe 441 attached to the tip of the pipe 51 is inserted into the first hole 113. The 1 / 8-inch pipe 441 inserted into the first hole 113 is connected to the flow path 112. Note that the pipe 51 and the 1 / 8-inch pipe 441 may be collectively referred to as the "pipe 51." As a result, the mixture that flows through the pipe 51 is introduced into the flow path 112. However, the pipe connected to the flow path 112 may be a pipe of a size or shape other than a 1 / 8-inch pipe.

[0082] The first hole 113 has a tapered portion 113T whose diameter becomes smaller as it advances toward the negative Z-direction, which is the flow path 112 side. Furthermore, the 1 / 8 inch piping 441 is preferably fitted into the first hole 113 via a connection ferrule that is pressure-deformed when it comes into contact with the tapered portion 113T of the first hole 113. A high-temperature, high-pressure mixture flows through the 1 / 8 inch piping 441. Therefore, by fitting the 1 / 8 inch piping 441 into the first hole 113 via the connection ferrule, the 1 / 8 inch piping 441 does not come off the first hole 113 even when a high-temperature, high-pressure mixture flows.

[0083] The region of the base 111 where the first hole 113 is provided may be heated by a heating mechanism (for example, a heating block). By providing the 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 100 has a block 114 on the tip side (positive side in the X direction) of the base 111. The block 114 is attached to the base 111 via screws 115a and 115b.

[0085] A second hole 116 is recessed in the tip surface of the block 114 (i.e., the tip surface of the housing portion 110) so as to be recessed toward the negative X-direction side, which is the side of the flow path 112. In this embodiment, the second hole 116 is formed along the X-direction. The nozzle portion 120 is inserted into the second hole 116. The second hole 116 is an example of a "hole."

[0086] The pressure of the mixture contained in housing 110 is preferably 60 MPa or less. The temperature of the mixture contained in housing 110 is preferably 250° C. or less, although this is not limitative.

[0087] <<Nozzle section>> The nozzle part 120 has a nozzle base 121 that extends along the X direction when inserted into the second hole part 116. A press-type connecting screw is formed on the outer periphery of the nozzle base 121. The thread groove of the connecting screw in the nozzle base 121 engages with the thread groove formed in the second hole part 116, so that the nozzle part 120 is fitted into the second hole part 116 in a pressed state.

[0088] A tubular nozzle pipe section 122 extending in the X direction is formed inside the nozzle base section 121. As shown in Fig. 3, the nozzle pipe section 122 has a first pipe section 122a that communicates with the tip of the flow path 112, and a second pipe section 122b that is concentric with the first pipe section 122a and is provided outside the first pipe section 122a. The tip of the second pipe section 122b corresponds to a nozzle hole 123 that discharges the mixture onto the substrate 12.

[0089] The nozzle pipe section 122 has a double pipe structure made up of a first pipe section 122a and a second pipe section 122b. Such a double pipe structure can increase the strength of the nozzle pipe section 122. In addition, the ejection stability of the mixture supplied from the flow channel 112 can be improved.

[0090] The diameter of the nozzle hole 123 is preferably 5 μm or more and 500 μm or less, more preferably 100 μm or more and 300 μm or less, and even more preferably 150 μm or more and 250 μm or less.

[0091] If the diameter of the nozzle hole 123 is less than 5 μm, it is not preferable because the diameter is too thin and stable ejection of the mixture may be hindered. Also, if the diameter of the nozzle hole 123 is more than 500 μm, it is not preferable because the thickness of the region of the nozzle part 120 excluding the nozzle hole 123 becomes thin and there is a possibility that it may not be able to withstand the pressure when ejecting the mixture.

[0092] The nozzle portion 120 also has a connection ferrule 124 provided on the outer periphery of the nozzle pipe portion 122. As shown in Figures 2 and 3, the connection ferrule 124 is a member made of, for example, stainless steel, and has a generally truncated cone shape whose diameter narrows as it advances toward the negative side in the X direction.

[0093] When the nozzle part 120 is fitted into the second hole part 116 in a pressed state, the connection ferrule 124 collides with the tapered portion 116T of the second hole part 116. After colliding with the tapered portion 116T, the connection ferrule 124 moves further toward the back of the second hole part 116 and is inserted into the tapered portion 116T. As a result, the connection ferrule 124 is deformed by pressure so as to be crushed by the tapered portion 116T of the second hole part 116. This restricts further movement of the connection ferrule 124. As a result, the nozzle part 120 is fitted into the second hole part 116 and is firmly fixed to the block 114.

[0094] Pressure resistance and durability can be improved by fixing the nozzle part 120 to the block 114 of the housing part 110 via the connecting ferrule 124. In particular, since a high-pressure mixture flows through the nozzle part 120, joining the nozzle part 120 and the housing part 110 via the connecting ferrule 124 is preferable.

[0095] <<Needle>> The needle 130 is inserted into the housing portion 110 and functions as a valve that opens and closes the flow path 112 of the housing portion 110 .

[0096] Specifically, as the needle 130 advances, the tip of the needle 130 blocks the extremely small hole 132 of the orifice 131 provided between the flow path 112 and the rear end of the nozzle pipe portion 122 of the nozzle portion 120. This closes the flow path 112. Next, as the needle 130 retreats, the tip of the needle 130 moves away from the orifice 131. This opens the extremely small hole 132 of the orifice 131, and the flow path 112 opens.

[0097] A desired amount of the mixture that has reached the flow path 112 can be supplied to the nozzle portion 120 side by opening and closing the flow path 112 in the needle 130. The response speed of the needle 130 (valve opening time) is preferably 100 μsec or less.

[0098] <<Drive mechanism>> The driving mechanism 140 is a mechanical part that is connected to the needle 130 and that moves the needle 130 forward and backward. Specifically, as shown in Fig. 2, the driving mechanism 140 has a long cylindrical extension bar 141 that connects to the rear end of the needle 130, and a piezoelectric actuator 142 that moves the extension bar 141 forward and backward at a predetermined speed.

[0099] The extension bar 141 is preferably made of a material with a low thermal expansion coefficient to avoid thermal expansion due to heat transfer from the needle in contact with the mixture. Examples of materials with a low thermal expansion coefficient include Invar, which is an alloy of iron and nickel, and Super Invar, which is an alloy of iron, nickel, and cobalt. Of these, Super Invar, which has an extremely low thermal expansion coefficient, is preferred.

[0100] A mixture having a temperature of, for example, about 250°C flows through the flow channel 112. The tip region of the needle 130 is inserted into the flow channel 112 and comes into contact with the mixture. The extension bar 141 is connected to the needle 130. Heat from the mixture is transferred to the extension bar 141 via the needle 130. If the extension bar 141 were to undergo significant thermal expansion, the range of movement of the extension bar 141 would change, and the range of movement of the needle 130 would also change. As a result, a desired amount of the mixture contained in the flow channel 112 may not be accurately supplied to the nozzle portion 120. By contrast, if the extension bar 141 is made of a material with a low thermal expansion coefficient, such as Super Invar, thermal expansion 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 to the nozzle portion 120.

[0101] Furthermore, if the extension bar 141 is made of a material that can suppress thermal expansion, such as Super Invar, the operational stability of the piezoelectric actuator 142 can be ensured.

[0102] The piezoelectric actuator 142 includes, for example, a piezoelectric element that expands and contracts in response to the application of a pulse-like voltage signal. In this embodiment, the piezoelectric actuator 142 expands and contracts in the X direction. Preferably, the piezoelectric actuator 142 is a ring actuator that is provided around the outer periphery of the extension bar 141. By using the piezoelectric actuator 142 as a ring actuator, it does not have any sharp corners and the load during operation is distributed evenly over the entire surface, thereby improving durability. Furthermore, the piezoelectric actuator 142 can be configured with a thin piezoelectric element layer, allowing for a large amount of displacement to be obtained at a low voltage.

[0103] In this embodiment, the actuator of the drive mechanism 140 is a piezoelectric actuator 142, but other types of actuators may also be used. However, from the viewpoint of high-speed response to achieve opening and closing operations of the valve in less than approximately 100 μsec, it is preferable to use a piezoelectric actuator 142.

[0104] <<Insulating flange>> The insulating flange 150 prevents heat transfer from the housing part 110 to the piezoelectric actuator 142. The material of the insulating flange 150 is not particularly limited, but it is preferably made of ceramics with high thermal insulation properties. By providing the insulating flange 150 between the housing part 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 Fig. 4 and Fig. 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 AA shown in Fig. 4.

[0106] 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 tip region of the flow path 112 near the orifice 131.

[0107] The divided paths 112a to 112d are arranged along the circumferential direction of the needle 130 and are formed by gaps extending radially outward from the outer circumferential wall 135 of the needle 130. Furthermore, boundary walls of adjacent divided paths, such as the boundary wall between the divided path 112a and the divided path 112b, the boundary wall between the divided path 112b and the divided path 112c, the boundary wall between the divided path 112c and the divided path 112d, and the boundary wall between the divided path 112d and the divided path 112a, come into contact with the outer circumferential wall 135 of the needle 130. This makes it possible to guide the needle 130 so that it remains positioned at the center of the flow path 112 even after moving back and forth. As a result, a desired amount of mixture can be accurately supplied to the nozzle portion 120. [Example]

[0108] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0109] Example 1 As a cloth-like substrate to which a functional agent was to be applied, PET knit (manufactured by Uni Seni Co., Ltd., fabric weight: 138 g / m 2 , yarn count: 75 / 72) was used. Disperse Blue 14 dye was used as a function-imparting agent.

[0110] Using the functionalized substrate manufacturing apparatus 1 shown in FIG. 1, 5 mg of Disperse Blue 14 was supplied to a 400 ml high-pressure vessel 6 at 135°C and 40 MPa and dissolved in supercritical carbon dioxide fluid. The substrate, cut to an 8 cm x 10 cm size, was placed on the stage of a conveying mechanism 14 and heated to a surface temperature of 150°C using a heating mechanism 15. Next, while the substrate was being conveyed at a speed of 15 mm / sec, a supercritical carbon dioxide fluid containing dissolved Disperse Blue 14 was ejected from a pulse valve 10 having a 100 μm diameter nozzle hole 123 in a gaseous and / or supercritical state and applied to the substrate. During ejection, the pulse valve 10 was heated and maintained at 145°C to prevent a decrease in temperature due to gas expansion. The substrate was then dyed by maintaining the heated state for 10 minutes, producing the functionalized substrate of Example 1.

[0111] (Comparative Example 1) The substrate used in Example 1, that is, the undyed fabric itself, was used as the functionalized substrate in Comparative Example 1.

[0112] (Comparative Example 2) 14 g of substrate was placed inside a 400 ml high-pressure vessel 6 in the functionalized substrate manufacturing apparatus 1 shown in FIG. 1 , and 42 mg of Disperse Blue 14 and supercritical carbon dioxide fluid were supplied to the high-pressure vessel 6 and mixed at 120°C and 25 MPa, followed by dyeing for 60 minutes at a bath ratio of 1:28 (mass ratio), thereby producing the functionalized substrate of Comparative Example 2.

[0113] (Comparative Example 3) In addition, 10 g of substrate was placed in a 400 ml high-pressure vessel of a mini-color dyeing machine (manufactured by Texam Giken Co., Ltd.) and dyed for 60 minutes at 130°C in a bath ratio of 1:30 (mass ratio) using a suspension of 30 mg of Disperse Blue 14 suspended in 300 mL of water. After dyeing, reduction cleaning was performed at 80°C for 20 minutes using an aqueous solution prepared by dissolving 1 g of surfactant or soaping agent Sunmol RC-700E Concentrate (manufactured by Nicca Chemical Co., Ltd.), 2 g of hydrosulfite, and 2 g of NaOH in 1 L of water, to produce a functionalized substrate for Comparative Example 3.

[0114] <Evaluation> For each functionalized substrate, the measurement of the surface oligomers and the evaluation of the measurement of the total oligomers were performed according to the following procedure.

[0115] <Measurement of surface oligomers> <<Extraction with tetrahydrofuran>> Pieces of each functionalized substrate cut into 1 cm × 1 cm were used as evaluation samples. One of the four equal parts of each evaluation sample was placed in a 10 ml vial, and about 5 ml of tetrahydrofuran (THF) was added. Ultrasonic treatment was performed at an initial temperature of 25 °C and 40 KHz for 30 minutes, and left overnight to obtain a THF extract. About 9.5 ml of acetonitrile was added to 1 ml of the THF extract to obtain an analytical sample for surface oligomer analysis. The oligomers extracted by this tetrahydrofuran extraction were regarded as the oligomers present on the surface of the functionalized substrate and subjected to subsequent HPLC analysis.

[0116] <<HPLC analysis>> Using the analytical sample for surface oligomer analysis, HPLC analysis was performed under the following HPLC conditions.

[0117] [HPLC conditions] · HPLC apparatus: ACQUITY UPLC H-Class system (manufactured by Waters) · Column: ACQUITY UPLC BEH C18 (manufactured by Waters, column: 50 × 2.1 mm i.d., particle size: 1.7 μm) · Column temperature: 40 °C · Mobile phase: Phase A: 10 mM ammonium formate aqueous solution, 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 to : 99 / 1 (Phase A / Phase B, volume ratio) · Sample injection volume: 5 μL · Sample temperature: 10 °C ·UV conditions: Absorption wavelength: 195 nm - 480 nm, Resolution: 1.2 nm

[0118] <<Quantification of Oligomers>> Regarding the method for calculating the quantitative value from the HPLC peak area, the quantitative value of the cyclic trimer (CDMP) of dimethyl phthalate, which is the oligomer to be measured, was obtained by conversion from the quantitative value of dimethyl phthalate (DMP).

[0119] Specifically, a calibration curve for dimethyl phthalate was calculated from the measurement results of the DMP standard solution. For the standard solution, approximately 60 mg of dimethyl phthalate was dissolved and diluted with acetonitrile in a 50 ml volumetric flask to prepare a DMP standard solution with a known concentration of 1200 ppm, and it was sequentially diluted and used. The content in terms of DMP conversion was calculated from the HPLC peak area corresponding to the oligomer, and then, assuming that the molar absorption coefficient of CDMP is three times that of DMP, the content in terms of DMP conversion was converted to the content of CDMP. The content of oligomers on the surface of each obtained functionalized substrate is shown in Table 1.

[0120] <Measurement of Total Oligomers> Regarding the total oligomers of each functionalized substrate, each functionalized substrate was completely dissolved in hexafluoroisopropanol, the polymer was precipitated with acetonitrile, and then the extract obtained by filtration with a filter was analyzed as the extract of the oligomers of the entire functionalized substrate.

[0121] <<Hexafluoropropanol Extraction>> One of the four equal parts of each evaluation sample was placed in a 10 ml vial, and approximately 0.6 ml of hexafluoropropanol was added. After standing for about 2 hours, approximately 9.4 ml of acetonitrile was added and filtered through a 0.2 μm PTFE filter for HPLC analysis.

[0122] <<Quantification of Total Oligomers>> Using the obtained extract, the total oligomer content of each functionalized substrate was calculated by performing the above <<HPLC Analysis>> and <<Quantification of Oligomers>>. The results are shown in Table 1.

[0123] [Table 1]

[0124] The results in Table 1 show that the batch-type anhydrous dyeing of Comparative Example 2 had a higher content of surface oligomers than Example 1 and Comparative Example 3. In Comparative Example 2 (batch-type anhydrous dyeing), oligomers were eluted from inside the substrate during batch dyeing, and furthermore, when the batch was released after dyeing, the solubility of the oligomers in carbon dioxide decreased, causing the oligomers to re-fix or migrate to the surface of the substrate, which is thought to be the cause of this phenomenon.

[0125] Comparing the water dyeing of Comparative Example 3 with the dyeing by the application step of Example 1, there is little difference in the content of surface oligomers, but there is a 0.15 mass% difference in the content of internal oligomers. In Comparative Example 3 (water dyeing), oligomers eluted from the inside of the substrate as in Comparative Example 2, but the amount eluted was less than in Comparative Example 2. In addition, in Comparative Example 3 (water dyeing), the dye liquor was removed with the oligomers eluted into the dye liquor, making it difficult for the oligomers to re-fix on the surface of the functionalized substrate. This suppresses the increase (re-fixation) of surface oligomers, and is thought to also result in a decrease in the content of internal oligomers.

[0126] On the other hand, in the dyeing using the application step of Example 1, although migration of oligomers occurs due to heating, the carbon dioxide density at the time of application to the substrate is low, so oligomer elution by the carbon dioxide fluid is unlikely to occur, and therefore the amount of oligomers moving to the surface of the functionalized substrate (surface oligomer content) was found to be small.

[0127] <Detection of surfactants> The following procedure was used to detect surfactants in the functionalized substrate of Comparative Example 3 (water-dyed). On the other hand, in Example 1, no surfactant treatment was performed, so no surfactant was detected. This confirmed that when a surfactant is used, it can be distinguished from components attached to the fabric.

[0128] <<Tetrahydrofuran Extraction>> As a control, RC-700E Conc. (manufactured by Nihon Kasei Chemical Co., Ltd.), the surfactant used in Comparative Example 3 (water dyeing), was diluted approximately 10,000-fold with acetonitrile and subjected to HPLC analysis. The functionalized substrate of Comparative Example 3 (water dyeing) with a size of 2 cm × 2 cm (0.0497 g) was further divided into four equal parts, placed in a 1.5 ml vial, and 1.2732 g of THF was added. Ultrasonic treatment was performed at an initial temperature of 25°C and 40 KHz for 30 minutes, and left overnight to obtain a THF extract. The obtained THF extract was diluted approximately 10-fold with acetonitrile, filtered through a 0.45 μm PTFE filter, and subjected to HPLC analysis.

[0129] <<LC-MS Analysis>> Using the THF extract as an analysis sample, LC-MS analysis was performed under the following LC-MS conditions and MS conditions.

[0130] [LC-MS Conditions] · Mass spectrometer: micrOTOF-QII (manufactured by Bruker Daltonics) · UHPLC device: Nexera XR (manufactured by Shimadzu Corporation) · Column: YMC-Triart C18 (manufactured by YMC Co., Ltd., column: 50 × 2.1 mm i.d., particle size: 1.9 μm, pore size: 12 nm) · Column temperature: 40°C · Mobile phase: Phase A: 10 mM ammonium formate aqueous solution, 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) · Sample injection volume: 10 μL · Ionization method: Electrospray ionization (ESI) · Detected ions: Positive ions · Source: End plate offset: -500V Capillary: 4500V Nebulizer: 2.0 bar Drying gas: 8.0L / min ·Drying temperature: 200℃ Calibration: Tuning mix ES-TOF (ESI) (Agilent Technologies)

[0131] [MS conditions] Mode: Wide Funnel 1: 300Vpp Funnel 2: 300Vpp Hexapole: 300Vpp Collision RF: 600Vpp Transfer time: 120μs Pre plus storage: 8μs

[0132] The spectra of the functionalized substrate of Comparative Example 3 and the control surfactant were compared by superimposing the three peaks detected in the elution time-mass graph (Figures 6 and 7). As a result, the same mass groups were confirmed, confirming that the surfactant remained in the functionalized substrate of Comparative Example 3.

[0133] From the above, it was found that the functionalized substrate obtained by a dyeing method using water (water dyeing) can be clearly distinguished from the functionalized substrate of this embodiment by examining the content of surfactants using LC-MS analysis or the like and confirming that the functionalized substrate of this embodiment does not substantially contain surfactants.

[0134] Example 2 In Example 1, the function-imparting agent (dye) was changed from Disperse Blue 14 to Disperse Orange 25, and the imparting step was carried out under the following conditions.

[0135] Using the functionalized substrate manufacturing apparatus 1 shown in FIG. 1, 5 mg of Disperse Orange 25 and 15 g of acetonitrile as an entrainer were supplied to a 400 ml high-pressure vessel 6 at 175°C and 25 MPa and dissolved in supercritical carbon dioxide fluid. The substrate, cut to an 8 cm x 10 cm size, was placed on the stage of the conveying mechanism 14 and heated to a surface temperature of 150°C using the heating mechanism 15. Next, while the substrate was being conveyed at a speed of 25 mm / sec, supercritical carbon dioxide fluid containing dissolved Disperse Blue 14 was ejected in a gaseous and / or supercritical state from a pulse valve 10 having a 100 μm diameter nozzle hole 123 and applied to a polymer molded body. The polymer molded body was dyed by maintaining the heated state for 10 minutes, producing the functionalized substrate of Example 2.

[0136] The functionalized substrate obtained in Example 2 was subjected to a washing fastness test based on JIS L 0844, No. A-2, and the results were grades 4-5 for discoloration after washing and grade 4 for staining after washing. Furthermore, a friction fastness test using a drying test based on the friction tester type II method of JIS L 0849 was also performed, and the results were equivalent to grades 3-4 for staining after friction. These tests were outsourced to the Kaken Test Center, a general incorporated foundation. From these results, it was confirmed that the functionalized substrate of Example 2 had a function-imparting agent inside the functionalized substrate.

[0137] Although the embodiments have been described above, the present invention is not limited to the above-described embodiments, and various modifications and improvements are possible within the scope of the present invention.

[0138] For example, aspects of the present invention are as follows. <1> A method for producing a functionalized substrate having a substrate and a function-imparting agent, comprising: The method for producing a functionalized substrate is characterized by including a step of discharging and applying a supercritical fluid in which the function-imparting agent is dissolved to the substrate in a gaseous state and / or a supercritical state. <2> The substrate is a polymer molded body. <1> 2. A method for producing a functionalized substrate according to claim 1. <3> The above-mentioned function-imparting agent is a dye. <1> or <2> 2. A method for producing a functionalized substrate according to claim 1. <4> The substrate is a cloth-like material. <1> from <3> 1. A method for producing a functionalized substrate according to any one of the above. <5> The function-imparting agent is at least one selected from the group consisting of an antiseptic, an antifungal agent, a waterproofing agent, and a conductive agent. <1> from <4> 1. A method for producing a functionalized substrate according to any one of the above. <6> the function-imparting agent has a first function-imparting agent and a second function-imparting agent, a first applying step of applying a supercritical fluid in which the first function-imparting agent is dissolved to the base material by discharging the supercritical fluid in a gas phase state; a second imparting step of discharging a supercritical fluid in a gas phase state, in which the second function-imparting agent is dissolved, onto the base material; The above-mentioned <1> from <5> 1. A method for producing a functionalized substrate according to any one of the above. <7> A functionalized substrate having a substrate and a function-imparting agent, Substantially free of surfactants The functionalized substrate is characterized in that the content of internal oligomers relative to all oligomers in the substrate is 50% by mass or more. <8> The substrate is a polymer molded body. <7> The functionalized substrate is as described in <9> The content of internal oligomers is 0.8% by mass or more. <7> or <8> 2. A method for producing a functionalized substrate according to claim 1. <10> The cloth-like <7> from <9> The functionalized substrate is any one of the above. <11> The above-mentioned function-imparting agent is a dye. <7> from <10> The functionalized substrate is any one of the above. <12> The colorfastness to washing based on JIS L 0844 A-2 is grade 4 or higher, and the staining fastness to washing is grade 3 or higher. The above-mentioned product has a rub fastness staining grade of 3-4 or higher in a dry test based on the rub tester type II method of JIS L 0849. <11> The functionalized substrate is as described in <13> The function-imparting agent is at least one selected from the group consisting of an antiseptic, an antifungal agent, a waterproofing agent, and a conductive agent. <7> from <12> The functionalized substrate is any one of the above. <14> The content of the function-imparting agent in the first region of the functionalized substrate is different from the content of the function-imparting agent in the second region of the functionalized substrate. <7> from <13> The functionalized substrate is any one of the above. <15> The function-imparting agent has a first function-imparting agent and a second function-imparting agent. <7> from <14> The functionalized substrate is any one of the above. <16> a high-pressure vessel for mixing the supercritical fluid and the function-imparting agent; a pulse valve that discharges the supercritical fluid in which the function-imparting agent is dissolved, supplied from the high-pressure vessel, in a gaseous state and / or a supercritical state; The functionalized substrate manufacturing apparatus has the following features. [Explanation of symbols]

[0139] 1. Functionalized substrate manufacturing equipment 6. High-pressure vessels 10,10a Pulse valve 12 Base material [Prior art documents] [Patent documents]

[0140] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-091805 [Patent Document 2] International Publication No. 2008 / 069041

Claims

1. A method for producing a functionalized substrate having a substrate and a function-imparting agent, comprising: A method for producing a functionalized substrate, comprising a step of discharging and applying a supercritical fluid having the function-imparting agent dissolved therein to the substrate in a gaseous state and / or a supercritical state.

2. The method for producing a functionalized substrate according to claim 1 , wherein the substrate is a polymer molded article.

3. The method for producing a functionalized substrate according to claim 1 , wherein the function-imparting agent is a dye.

4. The method for producing a functionalized substrate according to claim 1 , wherein the substrate is in the form of a cloth.

5. 2. The method for producing a functionalized substrate according to claim 1, wherein the function-imparting agent is at least one selected from the group consisting of an antiseptic, an antifungal agent, a waterproofing agent, and a conductive agent.

6. the function-imparting agent includes a first function-imparting agent and a second function-imparting agent, a first applying step of applying a supercritical fluid containing the first function-imparting agent to the base material by discharging the supercritical fluid in a gas phase state; a second applying step of applying a supercritical fluid containing the second function-imparting agent to the base material by discharging the supercritical fluid in a gas phase state; The method for producing a functionalized substrate according to claim 1 , comprising:

7. A functionalized substrate having a substrate and a function-imparting agent, Substantially free of surfactants A functionalized substrate, characterized in that the content of internal oligomers relative to all oligomers in the substrate is 50 mass % or more.

8. The functionalized substrate according to claim 7 , wherein the substrate is a polymer molded article.

9. The functionalized substrate according to claim 7 , wherein the content of the internal oligomer is 0.8% by mass or more.

10. The functionalized substrate according to claim 7, which is in the form of a cloth.

11. The functionalized substrate according to claim 7 , wherein the function-imparting agent is a dye.

12. The discoloration and fading in washing fastness according to JIS L 0844 A-2 is grade 4 or higher, and the staining in washing fastness is grade 3 or higher, 12. The functionalized substrate according to claim 11, wherein the staining resistance to friction measured by a dry test based on the friction tester type II method of JIS L 0849 is grade 3-4 or higher.

13. 8. The functionalized substrate according to claim 7, wherein the function-imparting agent is at least one selected from the group consisting of an antiseptic, an antifungal agent, a waterproofing agent, and a conductive agent.

14. The functionalized substrate according to claim 7 , wherein the content of the function-imparting agent in the first region of the functionalized substrate is different from the content of the function-imparting agent in the second region of the functionalized substrate.

15. The functionalized substrate according to claim 7 , wherein the functionalizing agent comprises a first functionalizing agent and a second functionalizing agent.

16. a high-pressure vessel for mixing the supercritical fluid and the function-imparting agent; a pulse valve that discharges the supercritical fluid in which the function-imparting agent is dissolved, supplied from the high-pressure vessel, in a gaseous state and / or a supercritical state; A manufacturing apparatus for a functionalized substrate comprising:

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