Compatibilizer for supercritical fluids and method for manufacturing fabrics using the same

Abstract

To provide a compatibility accelerator used for a supercritical fluid, which can improve adhesion of a dye, a functional agent, or the like to a workpiece.SOLUTION: The compatibility accelerator includes at least one of compounds selected from the group consisting a compound represented by a general formula (1): R1OOC-X-COOR2 (X denotes a 2-4C alkylene group or alkenylene group, R1 denotes a 1-4C alkyl group or phenyl group, and R2 denotes a 1-4C alkyl group or phenyl group) and a compound represented by a general formula (2): Y1-(AO)n-COR3 (AO denotes independently a 2-3C alkyleneoxy group, n denotes an integer of 1-3, Y1 denotes an R4O group or R5COO group, R4 denotes a 1-4C alkyl group or phenyl group, R5 denotes a 1-4C alkyl group or phenyl group, and R3 denotes a 1-4C alkyl group or phenyl group).SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present application discloses a compatibilizer for supercritical fluids and a method for producing fabrics using the same.

Background Art

[0002] Methods for coloring fiber products by dyeing processing and imparting functions to fiber products by functional processing are generally carried out by immersing the fiber products in an aqueous solution or an organic solvent containing dyes and functional agents. However, it is difficult to obtain a large amount of water in regions where water resources are scarce. In addition, there are also problems such as environmental damage caused by the discharge of contaminated wastewater and organic solvents after treatment. Therefore, it has been difficult to carry out such dyeing processing and functional processing in regions with strict environmental regulations. Accordingly, dyeing processing and functional processing using supercritical fluids have attracted attention as a method that produces almost no waste liquid.

[0003] For example, Patent Document 1 discloses a dyeing method for dyeing in a supercritical fluid, characterized in that a dye solution obtained by dissolving a dye in a solvent in advance is introduced into a dyeing tank containing an object to be dyed and the supercritical fluid.

[0004] Further, Patent Document 2 discloses a method for dyeing polyester fibers using a mixed solution of a polar organic solvent such as methanol or ethanol and water.

Prior Art Literature

Patent Literature

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problem to be Solved by the Invention

[0006] However, the method described in Patent Document 1 had the problem of low color density after dyeing. The mixture described in Patent Document 2 had the problem of being dangerous due to its low flash point, making it practically impossible to industrialize.

[0007] In dyeing and functional processing using supercritical fluids, the solubility of dyes and functional agents in the supercritical fluid changes significantly with temperature and pressure, which can result in the dyes and functional agents not completely dissolving in the supercritical fluid or precipitating. As a result, the fixation of dyes and functional agents to the workpiece is unstable, and unevenness may occur. Therefore, improving the amount of dye and functional agent adhering to the workpiece is a challenge.

[0008] The present inventors conducted extensive research on dyeing and functional processing using supercritical fluids and found that the dyeing methods disclosed in Patent Documents 1 and 2 resulted in insufficient dyeing due to the low solubility of dyes in supercritical carbon dioxide, which is a supercritical fluid. In addition, the dyeing method disclosed in Patent Document 2 uses low-boiling point organic solvents such as methanol and ethanol, making industrialization difficult.

[0009] The present invention aims to provide a compatibilizer for use in supercritical fluids that improves the adhesion of dyes, functional agents, and other chemicals to workpieces. [Means for solving the problem]

[0010] As one means of solving the above problems, this application discloses a compatibilizer for use in supercritical fluids, wherein the compatibilizer comprises at least one compound selected from the group consisting of compounds represented by the following general formula (1) and compounds represented by the following general formula (2). R 1 OOC-X-COOR 2 ...(1) Y 1 -(AO) n -COR 3 ...(2) In general formula (1), X is an alkylene group or alkenylene group having 2 to 4 carbon atoms, R 1 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, R 2 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, In general formula (2), each AO is independently an alkyleneoxy group having 2 to 3 carbon atoms, n is an integer of 1 to 3, Y 1 is R 4 O group or R 5 COO group, R 4 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, R 5 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, R 3 is an alkyl group having 1 to 4 carbon atoms or a phenyl group.

[0011] The present invention relates to the following items. Aspect 1 A compatibilizer for use in a supercritical fluid, A compatibilizer wherein said compatibilizer comprises at least one compound selected from the group consisting of compounds represented by the following general formula (1) and compounds represented by the following general formula (2). R 1 OOC-X-COOR 2 ···(1) Y 1 -(AO) n -COR 3 ···(2) In general formula (1), X is an alkylene group or alkenylene group having 2 to 4 carbon atoms, R 1 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, R 2 is an alkyl group having 1 to 4 carbon atoms or a phenyl group, In general formula (2), AO are each independently alkylene oxy groups having 2 to 3 carbon atoms. n is an integer from 1 to 3. Y 1 is R 4 O group or R 5 It is a COO group, R 4 This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. R 5 This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. R 3 This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. Appearance 2 A method for manufacturing fabrics using supercritical fluid, which involves using a supercritical fluid processing apparatus equipped with a processing tank, A first step involves introducing the compatibilizer described in claim 1 and at least one selected from the group consisting of dyes and functional agents into the supercritical fluid processing apparatus, setting the processing tank to a first temperature and a first pressure, and creating a supercritical state inside the processing tank. A second step involves increasing the pressure of the processing tank to a second pressure higher than the first pressure, and dissolving the compatibilizer in the supercritical fluid. A third step involves increasing the pressure of the processing tank to a third pressure higher than the second pressure and performing the processing at a third temperature. Includes, A method for manufacturing a fabric, wherein the third temperature is higher than the first temperature. Appearance 3 The method for manufacturing a fabric according to embodiment 2, wherein the first temperature is 31°C or higher and 150°C or lower, and the first pressure is 7.4 MPa or higher and 45 MPa or lower. Pattern 4 The method for manufacturing a fabric according to embodiment 2 or 3, wherein the second pressure is 11 MPa or more and 45 MPa or less. Appearance 5 A method for manufacturing a fabric according to any one of embodiments 2 to 4, wherein the third pressure is 20 MPa or more and 45 MPa or less, and the third temperature is 100°C or more and 150°C or less. [Effects of the Invention]

[0012] According to the present invention, by using a novel compatibilizer that improves the solubility of dyes and functional agents in supercritical fluids, the amount of chemicals adhering to the workpiece can be improved or stabilized. Furthermore, according to the present invention, a method for manufacturing fabrics using the compatibilizer can also be provided. [Brief explanation of the drawing]

[0013] [Figure 1] This is a schematic diagram illustrating the configuration of a supercritical fluid processing apparatus. [Figure 2] This is an example showing a state where the compatibilizer has spread across the entire visual window of a supercritical fluid processing device. [Figure 3] This is an example showing a state where the compatibilizer has not spread to a portion of the visual window of a supercritical fluid processing device. [Modes for carrying out the invention]

[0014] [Compatibilizer] One embodiment of the compatibilizer is a compatibilizer used in supercritical fluids, and comprises at least one compound selected from the group consisting of compounds represented by the following general formula (1) and compounds represented by the following general formula (2). R 1 OOC-X-COOR 2 ...(1) Y 1 -(AO) n -COR 3 ...(2) In general formula (1), X is an alkylene or alkenylene group having 2 to 4 carbon atoms. R 1 This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. R 2 This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. In general formula (2), AO are each independently alkylene oxy groups having 2 to 3 carbon atoms. n is an integer from 1 to 3. Y 1 is R4 O group or R 5 It is a COO group, R 4 This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. R 5 This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. R 3 This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0015] The compatibilizer preferably contains a compound represented by general formula (1) from the viewpoint of improving the solubility of the compatibilizer in supercritical fluids and the adhesion of chemicals such as dyes and functional agents to the workpiece.

[0016] As the supercritical fluid, supercritical carbon dioxide is preferred.

[0017] The compatibilizer is suitable for dyeing and functionalizing fibers using a supercritical fluid processing apparatus. The supercritical fluid processing apparatus is not particularly limited, and any supercritical fluid processing apparatus known in the art can be used.

[0018] <Compounds represented by general formula (1)> In the above general formula (1), X is an alkylene group or an alkenylene group having 2 to 4 carbon atoms. If X is a group other than these, the solubility of the compatibilizer in the supercritical fluid is insufficient. X may be a linear alkylene group or an alkenylene group, or a branched alkylene group or an alkenylene group. If X is an alkenylene group having 2 to 4 carbon atoms, it is preferable that the alkenylene group is a vinylene group. If X is an alkenylene group having 2 to 4 carbon atoms, the compound represented by the above general formula (1) may be either a cis or trans isomer. From the viewpoint of the solubility of the compatibilizer in the supercritical fluid, it is preferable that X is an alkylene group having 2 to 4 carbon atoms.

[0019] In the above general formula (1), R 1 R is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. 2 R is an alkyl group having 1 to 4 carbon atoms, or a phenyl group.1 and R 2 If the group is anything other than these, the solubility of dyes and functional agents in supercritical fluids is insufficient, and work efficiency decreases. 1 and R 2 These elements may be the same group or different groups. 1 and R 2 The alkyl group having 1 to 4 carbon atoms represented by may be a linear alkyl group or a branched alkyl group. From the viewpoint of adhesion of chemicals such as dyes and functional agents to the workpiece, 1 and R 2 The group is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group, an ethyl group, or an isobutyl group.

[0020] The compound represented by the above general formula (1) has a chemical structure corresponding to a dibasic acid diester. Specific examples of the compound represented by general formula (1) include dimethyl succinate, diethyl succinate, dimethyl glutarate, diethyl glutarate, dimethyl adipate, diethyl adipate, diisobutyl adipate, dimethyl 2-methylglutarate, dimethyl maleate, and diethyl maleate. Preferably, it is at least one selected from dimethyl adipate, diisobutyl adipate, dimethyl succinate, dimethyl glutarate, and dimethyl 2-methylglutarate, which exhibits an even higher compatibility effect.

[0021] The compounds represented by the above general formula (1) may be used individually or in combination of two or more.

[0022] <Compounds represented by general formula (2)> In the general formula (2) above, AO is independently an alkylene oxy group having 2 to 3 carbon atoms. That is, AO may be an ethylene oxy group, a propylene oxy group, or a combination thereof. When AO is an alkylene oxy group having 4 or more carbon atoms, the solubility of the compatibilizer in the supercritical fluid is insufficient.

[0023] In the general formula (2) above, n is an integer between 1 and 3. In particular, the compatibility effect is more easily exhibited when n is small. Preferably, n is 1 or 2.

[0024] In the above general formula (2), Y 1 is R 4 O group or R 5 It is a COO group, R 4 R is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. 5 R is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. In general formula (2), R 3 This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. 1 , and R 3 If the group is anything other than these, the solubility of the compatibilizer in the supercritical fluid decreases. 3 and R 4 These elements may be the same group or different groups. 3 , R 4 , and R 5 The alkyl group having 1 to 4 carbon atoms represented by may be a straight-chain alkyl group or a branched alkyl group.

[0025] The compounds represented by the above general formula (2) may be used individually or in combination of two or more.

[0026] <Other additives> To improve the effectiveness of the compatibilizer, the compatibilizer may contain at least one selected from the group consisting of a solvent other than the compound represented by general formula (1) and the compound represented by general formula (2), and a surfactant.

[0027] Examples of the solvents mentioned above include water and commonly used organic solvents. The solvents can be used individually or in combination of two or more.

[0028] Examples of organic solvents include alcohols such as methanol, ethanol, propanol, isopropanol, and butanol; glycols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol; ethers such as diethylene glycol monoalkyl ethers, triethylene glycol dialkyl ethers, propylene glycol dialkyl ethers, dipropylene glycol dialkyl ethers, 1,4-dioxane, and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, hexane, octane, and decane; petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; dimethylformamide; and N-methylpyrrolidone. Organic solvents can be used individually or in combination of two or more.

[0029] [Dyes and functional agents] Preferred dyes and functional agents used with compatibilizers include, for example, compounds used when treating polyester fibers.

[0030] <dye> Specific examples of dyes include direct dyes, reactive dyes, cationic dyes, disperse dyes, oil-soluble dyes, vat dyes, azo dyes, and sulfur dyes. Among these, disperse dyes are preferred. Dyes may be used individually or in combination of two or more types.

[0031] There are no particular restrictions on the type of disperse dye; either azo or quinone dyes may be used. Examples of disperse dyes include compounds classified as CIDisperse Black, CIDisperse Blue, CIDisperse Red, CIDisperse Orange, CIDisperse Yellow, CIDisperse Green, CIDisperse Violet, and CIDisperse Brown.

[0032] <Functional Agents> The functional agents are not particularly limited as long as they are commonly used as functional agents for textiles, and examples include flame retardants, ultraviolet absorbers, antibacterial agents, water absorbers, antistatic agents, and preservatives. Functional agents may be used alone or in combination of two or more types.

[0033] (Flame retardant) Examples of flame retardants include aromatic phosphate ester compounds such as triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, cresyl di2,6-xylenyl phosphate, 2-ethylhexyl diphenyl phosphate, naphthyl diphenyl phosphate, biphenyl diphenyl phosphate, 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, resorcinol bis(diphenyl phosphate), and 2-phenoxyethyl diphenyl phosphate; aromatic anilide phosphate compounds such as anilino diphenyl phosphate; and brominated compounds such as tris(dibromopropyl) isocyanurate (TBC). Flame retardants can be used individually or in combination of two or more.

[0034] (UV absorber) Examples of UV absorbers include benzotriazole-based UV absorbers such as 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol (Tinuvin 326), 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and 2-(2-hydroxy-5-methylphenyl)benzotriazole; 2-hydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrabutylbenzophenone. Examples include benzophenone-based UV absorbers such as droxybenzophenone; triazine-based UV absorbers such as 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol and 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine; and benzoxazinone-based UV absorbers such as 2,2'-(p-phenylene)di-3,1-benzoxazin-4-one. UV absorbers can be used individually or in combination of two or more.

[0035] (Antibacterial agent) Examples of antimicrobial agents include organic antimicrobial compounds and inorganic antimicrobial compounds. Examples of organic antimicrobial compounds include quinoline compounds such as 8-hydroxyquinoline; pyridine compounds such as 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, bis(2-pyridylthio-1-oxide)zinc, and (2-pyridylthio-1-oxide)sodium; and anilide compounds such as 3,4,4'-trichlorocarbanilide. Antimicrobial agents can be used alone or in combination of two or more.

[0036] (Water absorbent) Absorbent agents are compounds that can improve the water absorption of textile products. A specific example is polyester copolymer resin. Examples of polyester copolymer resins include copolymers of polycarboxylic acids such as adipic acid, terephthalic acid, isophthalic acid, and 5-sodium sulfisoisophthalic acid with polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, 1,4-butanediol, 1,6-hexanediol, and neopentanediol. Among these, from the viewpoint of water absorption, copolymers obtained by polymerizing terephthalic acid, or terephthalic acid and 5-sodium sulfosuccinic acid, with polyethylene glycol having a weight-average molecular weight of 2,000 to 6,000 as the polycarboxylic acid are preferred. Absorbent agents can be used alone or in combination of two or more.

[0037] [fiber] The fibers to be processed are not particularly limited, but are preferably chemical fibers. Examples of chemical fibers include semi-synthetic fibers such as acetate, and synthetic fibers such as polyester, polyamide, acrylic, and polyurethane such as spandex. The fibers preferably contain synthetic fibers, and are more preferably polyester fibers. In this disclosure, polyester fibers refer to fibers containing polyester fibers, and may consist only of polyester fibers, or may consist of polyester fibers and other fibers (blended, twisted, etc.).

[0038] There are no particular restrictions on the form of the fibers; they may be in the form of raw materials or semi-finished products such as cotton, yarn, cord, woven fabric, knitted fabric, or nonwoven fabric, or in the form of finished products such as clothing. Textile products consisting solely of polyester fibers, or textile products consisting of polyester fibers and other fibers (blended, twisted, woven, knitted, etc.) are preferred.

[0039] [Method of manufacturing pulp] In one embodiment, the fabric is manufactured using a supercritical fluid. The method for manufacturing the fabric using the supercritical fluid processing apparatus of one embodiment is as follows: A first step involves introducing a compatibilizer and at least one selected from the group consisting of dyes and functional agents into a supercritical fluid processing apparatus, setting the processing tank to a first temperature and a first pressure, and creating a supercritical state inside the processing tank. The second step involves increasing the pressure of the processing tank to a second pressure higher than the first pressure, and dissolving the compatibilizer in a supercritical fluid. A third step involves increasing the pressure of the processing tank to a third pressure higher than the second pressure and performing the processing at a third temperature. Including that, the third temperature is higher than the first temperature.

[0040] <Supercritical fluid> The supercritical fluid is not particularly limited as long as it is used in a supercritical fluid processing device. Preferably, it is supercritical carbon dioxide. <Supercritical Fluid Processing Equipment> As a supercritical fluid processing apparatus, a supercritical fluid processing apparatus equipped with a processing tank can be used. An exemplary supercritical fluid processing apparatus will be described in detail with reference to Figure 1. In Figure 1, the supercritical fluid processing apparatus comprises a carbon dioxide storage tank, a supply pump, a circulation pump, a dissolution tank, a processing tank, and a separation and recovery device. In Figure 1, L represents the liquid state, G represents the gaseous state, and Sc represents the supercritical state.

[0041] The supply pump is connected via piping to the outlet of the carbon dioxide storage tank and the inlet of the circulation pump, supplying carbon dioxide from the carbon dioxide storage tank to the circulation pump. The carbon dioxide storage tank stores carbon dioxide in liquid form, and by driving the supply pump, carbon dioxide can be supplied continuously.

[0042] A heating section (not shown) is provided between the supply pump and the circulation pump, and this heating section can bring the carbon dioxide that has passed through the supply pump to a supercritical state.

[0043] The circulation pump is connected to the outlet of the supply pump and is installed on the circulation path from the outlet of the treatment tank through the dissolution tank to the inlet of the treatment tank. Specifically, the circulation pump is connected to the first outlet of the treatment tank and the inlet of the dissolution tank. The circulation pump circulates the supercritical carbon dioxide present in the circulation path and within the treatment tank. This creates convection in the treatment tank during the treatment process.

[0044] The dissolution tank is connected to the outlet of the circulation pump and the inlet of the treatment tank. In the dissolution tank, a compatibilizer and at least one chemical used in the treatment, preferably selected from the group consisting of dyes and functional agents, are added and introduced into the treatment tank to be dissolved in supercritical carbon dioxide.

[0045] The processing tank comprises an inlet connected to the outlet of the dissolution tank, a first outlet connected to the inlet of the circulation pump, and a second outlet connected to the inlet of the separation and recovery device. In the processing tank, the fabric can be processed while wound on a bobbin. In this case, the processing tank is configured to house and hold the fabric together with the bobbin while it is wound on the bobbin. Supercritical carbon dioxide flowing into the processing tank from the inlet flows radially outward from the central axis of the bobbin and flows out from the first outlet. The processing tank processes the fabric in this state.

[0046] The separation and recovery unit is connected to the second outlet of the treatment tank and the inlet of the carbon dioxide storage tank, separating chemicals and other impurities from carbon dioxide. The vaporized carbon dioxide is discharged through a discharge valve (not shown) located in the separation and recovery unit. This allows for the efficient recovery of only carbon dioxide, making it possible to reuse the carbon dioxide used in the treatment. The recovered carbon dioxide is stored in the carbon dioxide storage tank.

[0047] Because the supply pump is located in a separate pipeline from the circulation path, after the processing of the fabric in the processing tank is complete, the circulation pump can circulate supercritical carbon dioxide through the processing tank and circulation path, while the supply pump can continuously supply fresh, pure supercritical carbon dioxide, free of chemicals, to the processing tank. This makes it possible to continuously clean the processing tank immediately following the processing process.

[0048] Furthermore, the supercritical fluid processing apparatus is not limited to the configuration described above; various modifications are possible as long as they have substantially the same configuration and produce similar effects.

[0049] <First step> The first step is to introduce a compatibilizer and at least one selected from the group consisting of dyes and functional agents into a supercritical fluid processing apparatus. The temperature and pressure of the processing tank in the first step (first temperature and first pressure) are set so that the inside of the processing tank becomes a supercritical state. That is, the first temperature and first pressure are preferably above the supercritical temperature and supercritical pressure, and can be set appropriately depending on the type of supercritical fluid used. For example, when supercritical carbon dioxide is used as the supercritical fluid, the temperature is preferably 31°C to 150°C and the pressure is preferably 7.4 MPa to 45 MPa. Under these conditions, carbon dioxide becomes supercritical carbon dioxide.

[0050] For example, when supercritical carbon dioxide is used as the supercritical fluid, the first temperature is preferably 31°C to 140°C, and the first pressure is preferably 7.4 MPa to 30 MPa. Specific examples of the first temperature and first pressure are, for example, 31°C and 7.4 MPa.

[0051] <Second step> The second step involves dissolving the compatibilizer in a supercritical fluid. The pressure in the treatment tank during the second step (second pressure) is higher than the pressure during the first step.

[0052] For example, when supercritical carbon dioxide is used as the supercritical fluid, the second pressure is, for example, 11 MPa.

[0053] For example, when supercritical carbon dioxide is used as the supercritical fluid, the temperature of the treatment tank in the second step (second temperature) is preferably 31°C to 150°C, and more preferably 50°C to 140°C. The second pressure is preferably 11 MPa to 45 MPa, and more preferably 11 MPa to 30 MPa. Within the above range, the compatibilizer dissolves in the supercritical carbon dioxide and fills the entire inside of the treatment tank.

[0054] <Third step> The third step is a process of performing treatments such as dyeing and functionalization. In the third step, the temperature of the treatment tank (third temperature) is higher than the first temperature, and the pressure of the treatment tank in the third step (third pressure) is higher than the second pressure. Preferably, the third temperature is higher than the second temperature. Preferably, the third step includes a step of increasing the pressure of the treatment tank to a third pressure higher than the second pressure and raising the temperature to a third temperature higher than the second temperature, and then performing the treatment.

[0055] For example, when supercritical carbon dioxide is used as the supercritical fluid, the third pressure is, for example, 25 MPa. The third temperature is preferably 100°C to 150°C, more preferably 100°C to 140°C, and even more preferably 100°C to 135°C. The third pressure is preferably 20 MPa to 45 MPa, and more preferably 20 MPa to 30 MPa.

[0056] The holding time after reaching the third temperature is not particularly limited and may be, for example, 40 minutes or more and 300 minutes or less.

[0057] <Dyes and functional agents> The dyes and functional agents described above can preferably be used as dyes and functional agents.

[0058] <Fabric> While not particularly limited, the fabrics include raw materials or semi-finished products such as woven fabrics, knitted fabrics, and nonwoven fabrics, as well as finished products such as clothing. Among these, textile products made solely of polyester fibers, or textile products made of polyester fibers and other fibers (blended, twisted, woven, knitted, etc.) are preferred.

[0059] <Ratio of compatibilizer mass to treatment tank volume> The ratio of the mass of the compatibilizer to the volume of the treatment tank is not particularly limited, but for example, it is 1 kg:10 L or more and 1 kg:5000 L or less, specifically, the ratio of the mass of the compatibilizer to the volume of the treatment tank is 1 kg:200 L. Preferably, the ratio of the mass of the compatibilizer to the volume of the treatment tank is 1 kg:50 L or more and 1 kg:1000 L or less, and more preferably, the ratio of the mass of the compatibilizer to the volume of the treatment tank is 1 kg:100 L or more and 1 kg:500 L or less. [Examples]

[0060] The effects of the technology of this disclosure will be described in more detail below with reference to examples, but the technology of this disclosure is not limited to the following specific examples.

[0061] The following describes in detail the solubility of compatibilizers in supercritical carbon dioxide, the solubility of dyes in supercritical carbon dioxide, and the test methods for measuring the color density of the dyed material.

[0062] [Test Method] <Solubility of compatibilizers in supercritical carbon dioxide> A supercritical fluid processing apparatus with a 50 mL processing tank volume and equipped with a visual inspection window was used. 2.0 mL of a compatibilizer was added to the processing tank, and the temperature and pressure were increased to 130°C and 25 MPa. Subsequently, the temperature was changed from 130°C to 60°C, and the behavior of the compatibilizer (solubility of the compatibilizer in supercritical carbon dioxide) was visually confirmed by a technician across the entire temperature range.

[0063] The solubility of the compatibilizer in supercritical carbon dioxide was evaluated according to the following criteria. Best: The compatibilizer is spread across the entire viewing window across the entire temperature range. Good: At some temperatures, the compatibilizer has spread across the entire viewing window. Defect: The compatibilizer is not spread across a portion of the viewing window across the entire temperature range. Figure 2 illustrates a state where the compatibilizer has spread across the entire viewing window. Figure 3 illustrates a state where the compatibilizer has not spread to a portion of the viewing window. The lower part of Figure 3 is the undissolved area.

[0064] <Solubility of dyes in supercritical carbon dioxide> Using a supercritical fluid processing device containing a compatibilizer and dye, 5.0 g of undyed woven tape (made of polyethylene terephthalate (PET)) wound onto a bobbin was exposed to supercritical carbon dioxide fluid along with the dye in a processing tank (volume 350 mL). The dye was a solid dye placed in the dissolution tank. CIDisperse Blue 301 (0.5% owf) was used as the dye. Note that %owf means weight percentage per 1 g of material to be dyed. The amount of dye added was 25 mg. The test conditions were: first temperature 31°C, first pressure 7.4 MPa, second temperature 130°C, second pressure 11 MPa, third temperature 130°C, third pressure 25 MPa. The dyeing time was 60 minutes. Afterwards, the temperature and pressure were reduced to 80°C or below, and atmospheric pressure was used, and the amount of residual dye was confirmed visually by a technician. A sample was evaluated as "good" if the amount of residual dye was similar to that of Example 1, and as "poor" if the amount of residual dye was similar to that of Comparative Example 1.

[0065] <Color density> Similar to the "Solubility of Dyes in Supercritical Carbon Dioxide" described above, woven tapes were dyed, and the color density of the dyed tapes was evaluated. The color density was evaluated using the L color space in the CIELAB color space as defined in JIS Z8781-4 (2013). * This was done by visual inspection or by measurement.

[0066] L * The values ​​were measured on dyed woven tapes using a Konica Minolta CM-3600A colorimeter under conditions of 20°C and 65% RH or less.* A smaller value indicates a darker color, L * A larger value indicates a lighter color. That is, L * A smaller value indicates better staining ability.

[0067] Visual evaluation of color density was performed using a grayscale for contamination (JIS L0805:2005) based on the following criteria. Best: Grayscale Grade 1 or lower Good: Grayscale, above Grade 1 and below Grades 2-3. Defective: Grayscale grade 2-3 or higher

[0068] <Example 1> As a compatibilizer, a mixture of dimethyl adipate, dimethyl succinate, and dimethyl glutarate in a 1:1:1 (mass ratio) was used to evaluate the solubility of the compatibilizer in supercritical carbon dioxide, the solubility of the dye in supercritical carbon dioxide, and the color density of the woven tape. The evaluation of color density was performed using L * The test was conducted based on the values. The amount of residual dye in the solubility test of dye in supercritical carbon dioxide in Example 1 was clearly less than the amount of residual dye in the solubility test of dye in supercritical carbon dioxide in Comparative Example 1. The results are shown in Table 1.

[0069] <Comparative Example 1> The solubility of the dye in supercritical carbon dioxide and the color density of the woven tape were evaluated using the same procedure as in Example 1, except that a compatibilizer was not used. The evaluation of color density was performed using L * The analysis was performed based on the values. The results are shown in Table 1.

[0070] <Examples 2-7, Comparative Examples 2-4> Except for using the compounds listed in Table 1 as compatibilizers, the solubility of the compatibilizer in supercritical carbon dioxide, the solubility of the dye in supercritical carbon dioxide, and the color density of the woven tape were evaluated using the same procedure as in Example 1. The color density was evaluated visually. The results are shown in Table 1.

[0071] [Table 1]

[0072] <Consideration> Examples 1-7 and Comparative Examples 2-4 show that a compatibilizer containing at least one compound selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (2) improves the solubility of dyes in supercritical carbon dioxide and the adhesion of dyes to fabrics. Examples 1-6 and Example 7 show that a compatibilizer containing a compound represented by general formula (1) exhibits particularly good effects.

[0073] In Example 1, the L* value was 56.3, which corresponds to "best" in the visual evaluation criteria for color density. In contrast, the L* value of Comparative Example 1 was 66.4, which corresponds to "poor" in the visual evaluation criteria for color density. In other words, regarding color density, Examples 1-6 were best, Example 7 was good, and Comparative Examples 1-4 were poor.

[0074] The reasons for this are as follows: Examples 1-6, which are the best, are due to the dibasic acid diester having a structure that is good for compatibility. Example 7, which is good, is due to the benzoate structure having the ability to make dyes and supercritical carbon dioxide compatible, but its performance is slightly inferior to that of the dibasic acid diester structure. Comparative Examples 2 and 3, which are poor, are due to the long carbon chain resulting in low solubility of the compatibilizer, and Comparative Example 4, which is also poor, is due to the molecular weight being too large resulting in low solubility of the compatibilizer.

[0075] Furthermore, in the method for manufacturing fabric using the above-mentioned compatibilizer and supercritical fluid, it has been found that by performing the following three steps in this order, the color density of the fabric can be improved compared to cases where only the third step is performed: a first step in which the above-mentioned compatibilizer and at least one selected from the group consisting of dyes and functional agents are introduced into a supercritical fluid processing apparatus, the processing tank is set to a first temperature and a first pressure, and the inside of the processing tank is brought into a supercritical state; a second step in which the processing tank is pressurized to a second pressure higher than the first pressure and the compatibilizer is dissolved in the supercritical fluid; and a third step in which the processing tank is pressurized to a third pressure higher than the second pressure and the processing is performed at a third temperature higher than the first temperature.

[0076] In addition, in the solubility test of the dye in supercritical carbon dioxide in Example 1, it was found that even when the amount of dye was changed from 0.5% owf to 3.0% owf, an improvement in the solubility of the dye could be obtained.

Claims

1. A compatibilizer used in the dyeing process of fibers using supercritical carbon dioxide, which improves the solubility of dyes in supercritical carbon dioxide, The compatibilizer comprises at least one compound selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). R １ OOC-X-COOR ２ ・・・(1) Y １ —(AO) ｎ —CO ３ ・・・(2) In general formula (1), X is an alkylene or alkenylene group having 2 to 4 carbon atoms. R １ This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. R ２ This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. In general formula (2), AO are each independently alkylene oxy groups having 2 to 3 carbon atoms. n is an integer between 1 and 3. Y １ is R ４ O group or R ５ COO group, R ４ This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. R ５ This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group. R ３ This is an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

2. A method for manufacturing fabrics using supercritical carbon dioxide and a supercritical fluid processing apparatus equipped with a processing tank, A first step involves introducing the compatibilizer described in claim 1 and a dye into the supercritical fluid processing apparatus, setting the processing tank to a first temperature and a first pressure, and creating a supercritical state inside the processing tank. A second step involves increasing the pressure of the processing tank to a second pressure higher than the first pressure, and dissolving the compatibilizer in the supercritical fluid. A third step involves increasing the pressure of the processing tank to a third pressure higher than the second pressure and performing the processing at a third temperature. Includes, A method for manufacturing a fabric, wherein the third temperature is higher than the first temperature.

3. The method for manufacturing a fabric according to claim 2, wherein the first temperature is 31°C or higher and 150°C or lower, and the first pressure is 7.4 MPa or higher and 45 MPa or lower.

4. The method for manufacturing a fabric according to claim 2 or 3, wherein the second pressure is 11 MPa or more and 45 MPa or less.

5. The method for manufacturing a fabric according to claim 2 or 3, wherein the third pressure is 20 MPa or more and 45 MPa or less, and the third temperature is 100°C or more and 150°C or less.

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