Textile products coated with sizing agent, sizing agent, method for manufacturing textile products coated with sizing agent, and method for manufacturing textile products.

Abstract

To provide a fiber product with a sizing agent that offers superior fiber convergence.SOLUTION: The present invention provides a fiber product with a sizing agent, where the sizing agent includes (A) at least one cellulose ether selected from the group consisting of alkyl cellulose, hydroxy alkyl cellulose, and hydroxyalkyl alkyl cellulose.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a sizing agent-coated textile product, a sizing agent, a method for producing a sizing agent-coated textile product, and a method for producing a textile product. [Background technology]

[0002] Generally, woven fabrics such as cotton products are made by the intertwining of warp and weft threads. Therefore, the process of making a fabric begins with separating the raw yarn into warp and weft threads. The separated raw yarn is then passed through various processes. Among these processes, the warp sizing process has a significant impact on the efficiency of the loom and the quality of the finished product. The sizing agent used in the sizing process is required to have various functions, such as increasing the cohesion of the fibers, suppressing fuzzing, and imparting physical properties such as tensile strength and abrasion resistance to the fibers. [Overview of the Initiative] [Problems that the invention aims to solve]

[0003] Conventionally, starch-based sizing agents have been used in the sizing process. However, in starch-based sizing agents, it is necessary to add components other than the main component, starch (cornstarch, etc.), such as wax, propylene glycol, and polyvinyl alcohol (PVA), in order to improve the convergence, smoothness, and flexibility of the fibers, which leads to complexity in formulation and increased costs. Furthermore, after diligent research by the present inventors, it was found that even when using starch-based sizing agents with the above-mentioned components other than starch added, there is room for improvement in the convergence of fibers, as shown in Comparative Example 1 described below. As described above, there is a desire for the realization of textile products with sizing agents that exhibit excellent fiber convergence properties.

[0004] The present invention aims to provide a textile product with a sizing agent that exhibits excellent fiber convergence properties. [Means for solving the problem]

[0005] The inventors of this invention conducted intensive research to solve the above problems and discovered that the above problems can be solved by using a binder containing a specific cellulose ether, thus completing the present invention. Specific embodiments of the present invention are as follows.

[0006] [1] Textiles coated with starch, The sizing agent comprises at least one cellulose ether (A) selected from the group consisting of alkylcellulose, hydroxyalkylcellulose, and hydroxyalkylalkylcellulose, wherein the sizing agent is used in the textile product with the sizing agent. [2] The sizing fiber article according to [1], wherein the cellulose ether (A) comprises at least one selected from the group consisting of methylcellulose, hydroxypropyl methylcellulose, and hydroxyethyl methylcellulose. [3] The sizing agent-coated fiber article according to [1] or [2], wherein the degree of substitution of the alkoxy group in the alkylcellulose or hydroxyalkylalkylcellulose is 1 to 3. [4] A textile product with a sizing agent according to any one of [1] to [3], wherein the viscosity of cellulose ether (A) when prepared as a 1% by weight or 5% by weight aqueous solution is 3 to 300 mPa·s. [5] The sizing fibrous product according to any one of [1] to [4], wherein the fibrous product includes cotton yarn or cotton fabric. [6] The sizing agent-coated textile article according to any one of [1] to [5], wherein the adhesion rate of the sizing agent to the sizing agent-coated textile article is 0.1 to 10% by weight. [7] A sizing agent comprising at least one cellulose ether (A) selected from the group consisting of alkylcellulose, hydroxyalkylcellulose, and hydroxyalkylalkylcellulose, for manufacturing a sizing agent-coated textile product according to any one of [1] to [6]. A method for manufacturing a sizing agent-coated textile product as described in any one of [8] [1] to [6], The method comprising the step of bringing a fibrous product into contact with a fluid containing the sizing agent to sizing the fibrous product. A method for producing a textile product from a sizing agent-coated textile product as described in any one of [9] [1] to [6], The method comprising the step of bringing a fluid containing supercritical carbon dioxide into contact with the sizing agent-coated textile product to remove the sizing agent from the sizing agent-coated textile product.

[10] The method according to [9], wherein the step of removing the adhesive is performed by batch processing or continuous processing. [Effects of the Invention]

[0007] The sizing agent-coated textile product of the present invention exhibits excellent fiber convergence properties. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a temperature-pressure phase diagram of carbon dioxide. [Figure 2] Figure 2 is an SEM image of cotton yarn without any sizing agent applied. [Figure 3] Figure 3 is a SEM image of cotton yarn with starch paste attached. [Figure 4] Figure 4 is an SEM image of cotton yarn to which cellulose ether (1) (methylcellulose) has been attached. [Figure 5] Figure 5 shows an overview of the equipment used for processing with a fluid containing supercritical carbon dioxide. [Figure 6] Figure 6(a) shows the jig with the fabric wrapped around it. Figure 6(b) shows the outer cylinder with the paper wiper wrapped around it. [Figure 7] Figure 7 shows the jig with cotton thread wrapped around it. [Figure 8] Figure 8 is an SEM image of the fabric coated with cellulose ether (3) (hydroxypropyl methylcellulose) before the desizing treatment, showing the sizing agent still attached. [Figure 9] Figure 9 is an SEM image of the fabric after desizing treatment, with cellulose ether (3) (hydroxypropyl methylcellulose) attached. [Figure 10] Figure 10 is a photograph of the fabric after the water wettability evaluation.

Best Mode for Carrying Out the Invention

[0009] In this specification, when expressing a numerical range using "X to Y", the range shall include the numerical values at both ends.

[0010] Hereinafter, the fiber product with paste, the paste, the method for manufacturing the fiber product with paste, and the method for manufacturing the fiber product of the present invention will be described.

[0011] 1. Fiber Product with Paste The fiber product with paste of the present invention is the fiber product with paste, wherein the paste contains at least one cellulose ether (A) selected from the group consisting of alkyl cellulose, hydroxyalkyl cellulose, and hydroxyalkyl alkyl cellulose. The fiber product with paste of the present invention is excellent in the convergence of fibers. In some cases, the fiber product with paste of the present embodiment can enhance the fiber convergence without excessively increasing the adhesion amount of the paste, or the fiber product with paste of the present embodiment can exhibit high tensile strength, or the fiber product with paste of the present embodiment has high durability against friction and is unlikely to cause a decrease in tensile strength even after a friction test.

[0012] (Paste) The paste may further contain components other than the cellulose ether (A) described above, or may not contain components other than the cellulose ether (A) (the paste may be composed of the cellulose ether (A) described above). In this specification, "not containing" a specific component means that the component is not intentionally added, and does not exclude a form in which the component is contained as an impurity. The components other than the cellulose ether (A) described above are not particularly limited, but may include or consist of corn starch, wax, propylene glycol, polyvinyl alcohol (PVA), or a combination of two or more of these. On the other hand, in the sizing agent-coated textile product of this embodiment, even if the sizing agent consists of the cellulose ether (A) without adding any other components, the fiber convergence can be improved. As described above, in conventional sizing agents containing starch paste, it is necessary to add components other than starch in order to improve the convergence, smoothness, flexibility, etc., of the fibers, and the cellulose ether (A) has properties that conventional starch paste does not have. Since it is not necessary to add any components other than the cellulose ether (A), the sizing agent-coated textile product of this embodiment does not require complex formulation, improving manufacturing efficiency and reducing costs.

[0013] The adhesion rate (amount of adhesive) of the adhesive to the adhesive-treated textile is not particularly limited, but is preferably 0.1 to 10% by weight, more preferably 1 to 8% by weight, and most preferably 3 to 7% by weight. When the adhesion rate of the adhesive is within the above numerical range, pilling due to friction between threads or friction between threads and metal is less likely to occur, and thread breakage is reduced, thus improving efficiency during weaving. The amount of adhesive to be applied to the adhesive-treated textile can be calculated based on the method and procedure described in (4-2) of 1. in [Examples] below.

[0014] The sizing agent (or fluid containing the sizing agent) is not particularly limited, but may not contain any pigments. Examples of such pigments include dyes, pigments, or mixtures thereof. The sizing agent is not particularly limited, but it can be any sizing agent other than printing sizing agent (sizing agent for printing). An example of such a sizing agent other than printing sizing agent is a sizing agent for the warp threads of textiles.

[0015] (Cellulose ether (A)) Alkylcellulose is a type of cellulose ether and can be produced by reacting cellulose with an etherifying agent. Alkylcellulose is a compound obtained by substituting some or all of the hydrogen atoms of the hydroxyl group (-OH) of cellulose with alkyl groups (-R), thereby converting it into an alkoxy group (-OR). Unalkylated cellulose is insoluble in water, but alkylation, which reduces the number of hydroxyl groups, weakens the hydrogen bonds between the hydroxyl groups, making it water-soluble. Alkylcellulose is not particularly limited, but may include or consist of methylcellulose, ethylcellulose, or a combination thereof. Of these, methylcellulose is preferred, as using methylcellulose allows for sizing in an aqueous system, which reduces costs, and also facilitates desizing with supercritical carbon dioxide, as described later.

[0016] Hydroxyalkylcellulose is a compound obtained by substituting some or all of the hydrogen atoms in the hydroxyl group (-OH) of cellulose with a hydroxyalkyl group, thereby converting it into a hydroxyalkoxy group. Hydroxyalkylcellulose may include, but is not limited to, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, or a combination thereof.

[0017] Hydroxyalkylalkylcellulose is a compound obtained by substituting some or all of the hydrogen atoms of the hydroxyl group (-OH) of cellulose with alkyl groups and hydroxyalkyl groups, thereby converting them into alkoxy groups and hydroxyalkoxy groups. Hydroxyalkylalkylcellulose is not particularly limited, but may include or consist of hydroxypropyl methylcellulose, hydroxyethyl methylcellulose, or a combination thereof. Of these, hydroxypropyl methylcellulose is preferred, as using hydroxypropyl methylcellulose allows for sizing in an aqueous system, which reduces costs, and also facilitates desizing with supercritical carbon dioxide, as described later.

[0018] The cellulose ether (A) described above is not particularly limited, but may include or consist of at least one selected from the group consisting of methylcellulose, hydroxypropyl methylcellulose, and hydroxyethyl methylcellulose. One or more of these compounds can be used as cellulose ether (A).

[0019] The degree of substitution of alkoxy groups in alkylcellulose and / or hydroxyalkylalkylcellulose (the average number of alkoxy groups per glucose ring unit of cellulose) is not particularly limited, but is preferably 1 to 3, more preferably 1.2 to 2.5, and most preferably 1.4 to 1.9. When the degree of substitution of alkoxy groups is within the above numerical range, the concentration and amount of sizing agent can be kept to a minimum while allowing for good penetration into the yarn and improving weaving efficiency. The degree of substitution of the alkoxy group can be the same as the degree of substitution of the methoxy group. For methylcellulose, the degree of substitution of the methoxy group is most preferably 1.64 to 1.92. For hydroxypropyl methylcellulose, the degree of substitution of the methoxy group is most preferably 1.79 to 2.04.

[0020] The number of moles of hydroxyalkoxy groups substituted in hydroxyalkylcellulose and / or hydroxyalkylalkylcellulose is not particularly limited, but is preferably 0.1 to 0.5, more preferably 0.15 to 0.4, and most preferably 0.2 to 0.35. When the number of moles of hydroxyalkoxy groups substituted is within the above numerical range, the concentration and amount of sizing agent can be minimized while allowing for good penetration into the yarn and improving weaving efficiency. The most preferred number of substituted hydroxypropoxy groups is 0.18 to 0.34. In this specification, the number of substituted moles of hydroxyalkoxy groups refers to the average number of moles of hydroxyalkoxy groups added per glucose ring unit of cellulose. The numerical range for the degree of substitution of the methoxy group and the numerical range for the number of substituted moles of the hydroxyalkoxy group can be combined in any way.

[0021] The weight-average molecular weight of cellulose ether (A) is not particularly limited, but is preferably 20,000 to 100,000, more preferably 30,000 to 90,000, and most preferably 50,000 to 80,000. When the weight-average molecular weight of cellulose ether (A) is within the above numerical range, the concentration and amount of sizing agent can be minimized while allowing for good penetration into the yarn and leading to improved weaving efficiency. The weight-average molecular weight of cellulose ether (A) can be measured by GPC using a GPC instrument (integrated instrument, manufactured by Tosoh Corporation, HLC®-8420GPC) (column: SB-806MHQ 40℃, guard column: SB-G6B, both manufactured by Resonaq Corporation) under the following conditions: solvent and eluent: 0.1M NaNO3 1.0 ml / min, injection volume: 100 μl.

[0022] The viscosity of cellulose ether (A) is not particularly limited, but when it is a 1% by weight aqueous solution, it is preferably 3 to 300 mPa·s, more preferably 30 to 200 mPa·s, and most preferably 50 to 150 mPa·s. When the viscosity of methylcellulose is within the above numerical range, the concentration and amount of sizing agent can be kept to a minimum while allowing for good penetration into the yarn and leading to improved weaving efficiency. Furthermore, the viscosity of cellulose ether (A) is not particularly limited, but when it is a 5% by weight aqueous solution, it is preferably 3 to 300 mPa·s, more preferably 30 to 200 mPa·s, and most preferably 50 to 150 mPa·s. When the viscosity of methylcellulose is within the above numerical range, the concentration and amount of sizing agent can be kept to a minimum, while the penetration into the yarn is good, leading to improved weaving efficiency. The viscosity range for a 1% by weight aqueous solution can be applied to, for example, methylcellulose, and the viscosity range for a 5% by weight aqueous solution can be applied to, for example, hydroxypropylmethylcellulose. The viscosity of cellulose ether (A) can be calculated based on the method described in (4-1) of 1. in the [Examples] section below.

[0023] The cellulose ether (A) content in the sizing agent can be 100% by weight (the sizing agent consists of cellulose ether (A)), in which case, as described above, the fiber convergence can be improved while simplifying the formulation and suppressing costs. The cellulose ether (A) content in the sizing agent can be 80% or more by weight, 90% or more by weight, or 95% or more by weight. Alternatively, the cellulose ether (A) content in the sizing agent can be 100% or less by weight. The above numerical ranges can be combined arbitrarily.

[0024] (Textiles) The textile product is not particularly limited, but examples include fibers, yarns, and fabrics. Fibers include tow before they become yarn. Yarns are not particularly limited, but examples include spun yarns, filament yarns, and blended yarns and spun yarns made by twisting these together. Fabrics include woven or knitted fabrics made from yarn, or nonwoven fabrics and felts. In this embodiment, it is preferable to use yarn as the textile product, in which case the yarn treated with the sizing agent obtained by this method can be subjected to the subsequent weaving process. Textile products may include or consist of cotton yarn or cotton fabric.

[0025] The type of yarn is not particularly limited, but for example, natural fibers such as plant fibers like cotton and linen, animal fibers such as silk and wool, synthetic fibers such as polyester and acrylic, semi-synthetic fibers such as acetate, triacetate and Promix, regenerated fibers such as rayon, polynosic, cupro and lyocell, and chemical fibers such as glass fibers, metal fibers and carbon fibers can be used. Two or more of these yarns may be blended or twisted together. Furthermore, these yarns may be single yarns, double yarns, triple yarns, or yarns made by twisting together four or more strands. In this embodiment, it is preferable to use cotton yarn from the viewpoint of the feel of the towel against the skin. The type of fabric is not particularly limited, but it can be the same as the type of yarn mentioned above.

[0026] The sizing-treated textile product is not particularly limited, but may be sizing-treated yarn or sizing-treated fabric. The above-mentioned sizing agent-treated yarn can be used as warp threads in a woven fabric, although this is not a particular limitation. The above-mentioned sizing-treated fabric is not particularly limited, but can be a woven fabric comprising warp threads with sizing containing the cellulose ether (A) attached (with sizing adhering to them) and weft threads without sizing containing the cellulose ether (A) attached. Here, weft threads without sizing containing the cellulose ether (A) attached mean weft threads to which the sizing has not been actively attached. Therefore, the weft threads without sizing containing the cellulose ether (A) attached may also include a configuration in which the warp threads with sizing containing the cellulose ether (A) come into contact with the weft threads, and the sizing from the warp threads is transferred to the weft threads.

[0027] 2. Dough starter The present invention provides a sizing agent for producing the sizing agent-coated textile product described in 1. above, comprising at least one cellulose ether (A) selected from the group consisting of alkylcellulose, hydroxyalkylcellulose, and hydroxyalkylalkylcellulose. The adhesive of this embodiment can keep the BOD and / or COD values ​​in solution lower than conventional starch pastes, thereby suppressing water pollution. In the sizing agent of this embodiment, the types and contents of the sizing agent, cellulose ether (A), and textiles can be similarly adopted to those described in 1. above.

[0028] As mentioned in item 1 above, the sizing agent (or fluid containing the sizing agent) may not contain dyes. The sizing agent may be one other than a printing sizing agent. An example of such a sizing agent other than a printing sizing agent is a sizing agent for the warp threads of textiles.

[0029] 3. Method for manufacturing textile products with sizing agent The method for producing a sizing agent-coated textile product according to the present invention is: A method for manufacturing a sizing agent-coated textile product as described in item 1 above, The process includes bringing a fluid containing the aforementioned sizing agent into contact with a textile product to apply sizing to the textile product.

[0030] In the method of this embodiment, the types and contents of the sizing agent, cellulose ether (A), and fiber product can be similarly adopted to those described in 1. above.

[0031] In this embodiment, the processing conditions for bringing the fluid containing the sizing agent into contact with the textile product are not particularly limited, but from the viewpoint of improving sizing performance, the temperature can be in the range of 0 to 100°C, preferably in the range of 0 to 75°C, and most preferably in the range of 0 to 55°C. Also from the viewpoint of improving sizing performance, the pressure is preferably 0.01 to 0.2 MPa. Furthermore, from the viewpoint of improving sizing performance, the processing time is preferably about 60 minutes per 450 kg of textile product. The process of bringing a fluid containing a sizing agent into contact with the textile product can be carried out by batch processing.

[0032] The amount of sizing agent used is not particularly limited, but for example, when using cotton yarn as a textile product, it is preferable to use 0.03 to 0.07 g of sizing agent per gram of cotton yarn from the viewpoint of improving sizing properties.

[0033] The content of cellulose ether (A) in the fluid containing the sizing agent is not particularly limited, but is preferably 0.1 to 10% by weight, more preferably 0.5 to 7% by weight, and most preferably 1 to 5% by weight. When the content of cellulose ether (A) in the fluid is within the above numerical range, the concentration and amount of sizing agent are minimized, while the penetration into the yarn is good, leading to improved weaving efficiency.

[0034] In this embodiment, the fluid containing the adhesive is not particularly limited, but may further contain a solvent. The above solvent is not particularly limited, but may include or consist of water, aqueous solvents such as glycol ethers and lower alcohols, glycerin, polyethylene glycol, polypropylene glycol, DMSO, DMF, benzyl alcohol, N-methyl-2-pyrrolidone, or a combination of two or more of these. Of these, the inclusion of water is preferable. The inclusion of water in the fluid provides excellent solubility and appropriate viscosity. The glycol ether solvent described above is not particularly limited, but may include or consist of ethylene glycol monobutyl ether (2-butoxyethanol) (EGME), diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, 2-methylpentane-2,4-diol, diethylene glycol monohexyl ether, diethylene glycol dibutyl ether, triethylene glycol monobutyl ether, or a combination of two or more of these. Among these, the inclusion of EGME is preferred. The lower alcohols mentioned above are not particularly limited, but may include or consist of methanol, ethanol, or a combination thereof. The solvent content in the fluid containing the binder is not particularly limited, but is preferably 50 to 99% by weight, more preferably 65 to 95% by weight, and most preferably 80 to 95% by weight. When the solvent content in the fluid containing the binder is within the above numerical range, the solubility of the solids is improved.

[0035] In this embodiment, when a solvent is used, the solvent can be delivered into the processing container.

[0036] When using a solvent, the ratio (moles) of solvent to 1-5 g of adhesive is not particularly limited, but 1-6 moles is preferred from the viewpoint of improving adhesive properties.

[0037] The method of this embodiment can be used as a sizing process, which is one of the textile processing steps, and can also be used in combination with other textile processing steps such as spinning, weaving, desizing / scouring / bleaching, dyeing, and finishing. Furthermore, the method for manufacturing sizing-coated textile products of this embodiment can be combined with the method for manufacturing textile products from sizing-coated textile products described later to form a single method or manufacturing method.

[0038] The method of this embodiment may include or consist of a step of applying sizing to the textile product by bringing a fluid containing the sizing agent into contact with the yarn to apply sizing to the yarn. In this case, the method of this embodiment may further include a step of forming a fabric using the yarn with the sizing agent applied, thereby forming a sizing-coated fabric. Furthermore, in this case, the method of this embodiment may include or consist of a step of forming a woven fabric using the yarn with the sizing agent applied as warp threads, thereby forming a sizing-coated woven fabric.

[0039] 4. Method for manufacturing textile products from sizing-coated textile products The present invention provides a method for producing textile products from sizing-coated textile products, A method for producing textile products from sizing agents-coated textile products as described in 1. above, The process includes a step of removing the starch from the starched textile by bringing a fluid containing supercritical carbon dioxide into contact with the starched textile. The method for producing textile products from sizing-coated textile products according to this embodiment allows for efficient removal of the sizing agent, resulting in textile products with excellent water wettability.

[0040] In the method of this embodiment, the types and contents of the sizing agent, cellulose ether (A), and fiber product can be similarly adopted to those described in 1. above. In this embodiment, from the viewpoint of the feel of the towel against the skin, it is preferable to use cotton yarn as the fiber.

[0041] In this embodiment, the sizing agent-coated textile product is not particularly limited, but one obtained by the method for producing the sizing agent-coated textile product described in 3. above can be used.

[0042] Now, let's discuss supercritical carbon dioxide. It is known that fiber processing is performed using supercritical carbon dioxide. The supercritical state is achieved when the critical temperature (Tc) and critical pressure (Tp) specific to each compound are exceeded. This state is called a supercritical fluid and has properties intermediate between gas and liquid. As shown in Figure 1, carbon dioxide can achieve a supercritical state under relatively mild conditions, with a Tc of 31.1°C and a Tp of 7.38 MPa, and has advantages such as being non-explosive, non-toxic, highly safe, inexpensive, and readily available. Furthermore, supercritical carbon dioxide has the following characteristics: (1) near the critical temperature, its density changes greatly with even slight changes in pressure; (2) due to its low viscosity and high diffusivity, it has excellent transport properties and high penetration power into materials; (3) it has high thermal conductivity and a fast heat transfer rate; (4) it has a fast reaction rate due to the solvation effect; (5) its dielectric constant is lower than that of water and is similar to that of ordinary nonpolar organic solvents, making it a good solvent for nonpolar organic substances; and (6) it is possible to recover and reuse the carbon dioxide.

[0043] In this embodiment, the processing conditions for bringing a fluid containing supercritical carbon dioxide into contact with a sizing agent-coated textile product are not particularly limited. However, from the viewpoint of improving desizing properties, a temperature of 31 to 150°C or 40 to 120°C can be used, a pressure of 8 to 25 MPa or 10 to 25 MPa can be used, and a time of 30 to 800 minutes or 120 to 180 minutes can be used. In this embodiment, the process of removing the adhesive can be carried out by batch processing or continuous processing.

[0044] In this embodiment, the fluid containing supercritical carbon dioxide may further contain a cosolvent. The inclusion of a cosolvent in the fluid improves the solubility of the adhesive in the solvent (containing supercritical carbon dioxide and the cosolvent), thereby improving its de-adhesion properties. The co-solvent is not particularly limited, and any solvent described in section 3 above can be used, but glycol ether solvents, especially EGME, are preferred. By using the solvent described in section 3 above as the co-solvent, the solubility of the adhesive in the solvent (including supercritical carbon dioxide and the co-solvent) can be improved, thereby improving the de-adhesion properties. This effect is particularly pronounced when EGME is used as the co-solvent.

[0045] In this embodiment, when a co-solvent is used, the co-solvent can be supplied to the processing container separately from the supercritical carbon dioxide.

[0046] In this embodiment, when the desizing process is carried out by batch processing and a cosolvent is used, the ratio (mol%) of the cosolvent to supercritical carbon dioxide is not particularly limited, but from the viewpoint of improving the solubility of the adhesive in the solvent and thereby improving desizing performance, 0.1 to 2 mol% is preferred. The volume ratio of supercritical carbon dioxide to cosolvent is not particularly limited, but is preferably 400:1 to 10:1, more preferably 300:1 to 25:1, and most preferably 200:1 to 40:1. The volume ratio of supercritical carbon dioxide to cosolvent can also be 150:1 to 50:1, 100:1 to 60:1, or 90:1 to 70:1.

[0047] In this embodiment, when the desizing process is carried out by continuous processing, the flow rate of supercritical carbon dioxide into the processing container is not particularly limited, but from the viewpoint of improving the solubility of the sizing agent in the solvent and improving desizing performance, 50 ml to 2000 ml per gram of fiber is preferred, and 100 ml to 1500 ml is more preferred.

[0048] In this embodiment, when the desizing process is carried out by a continuous process and a co-solvent is used, the flow rate of the co-solvent to the processing container is not particularly limited, but is preferably 1 ml to 500 ml per gram of fiber, and more preferably 10 ml to 400 ml.

[0049] The percentage of adhesive removed after de-adhesive In the method of this embodiment, the solubility of the adhesive in a fluid containing supercritical carbon dioxide (amount of adhesive dissolved (g) / volume of fluid containing supercritical carbon dioxide (ml)) is not particularly limited, but is preferably 0.0001 to 0.01 g / ml, more preferably 0.001 to 0.008 g / ml, and most preferably 0.002 to 0.006 g / ml. The solubility of the adhesive in a fluid containing supercritical carbon dioxide is not particularly limited, but is 1 × 10 -5 g / ml or more, 1×10 -4 g / ml or more, or 1 × 10 -3 It can be g / ml or higher. The solubility of the adhesive in a fluid containing supercritical carbon dioxide is not particularly limited, but is 1 g / ml or less, or 1 × 10⁻⁶ -1 g / ml or less, or 1 × 10 -2 The value can be less than or equal to g / ml. The above numerical ranges can be combined in any way.

[0050] In this embodiment, the step of removing the starch may include moving the starched textile product with power. By moving the starched textile product with power, a kneading effect can be applied to the entire starched textile product (fabric), improving the starch removal properties. The power source is not particularly limited, but wind power, electricity, etc. can be used, and wind power is preferred among these.

[0051] The method of this embodiment can be used as a desizing process, which is one of the textile processing steps, and can also be used in combination with other textile processing steps such as spinning, weaving, sizing, scouring / bleaching, dyeing, and finishing. Furthermore, the method of producing textile products from sizing-treated textile products of this embodiment can be combined with the above-described method for producing sizing-treated textile products to form a single method or manufacturing method.

[0052] The present invention will be described in detail below with reference to examples, but the present invention is not limited to what is described in the examples. [Examples]

[0053] 1. Measurement of physical properties or observation of surface condition of sizing agents or sizing-coated textile products. (1) Preparation of aqueous solution containing a thickening agent The adhesives used are listed below. • Cellulose ether (1): Metroze® SM-1500 (methylcellulose, weight-average molecular weight: 90,000, degree of methoxy group substitution: 1.8, manufactured by Shin-Etsu Chemical Co., Ltd.) • Cellulose ether (2): Metroze® 60SH-06 (Hydroxypropyl methylcellulose, weight-average molecular weight: 80000, degree of methoxy group substitution: 1.9, number of substituted hydroxypropoxy groups: 0.25, manufactured by Shin-Etsu Chemical Co., Ltd.) • Starch paste: A paste containing cornstarch (weight-average molecular weight: 500,000-1,000,000), which is the main component of the paste, and additives (content of each component relative to the total paste: wax 2% by weight, glycerin 1% by weight, small amount of PVA added).

[0054] [Example 1] Boiling water was added to the above cellulose ether (1) to achieve a dilution ratio of 40 times by weight of the cellulose ether, and the resulting dilution was stirred for a certain period of time. After stirring, room temperature water was added to the diluted solution to achieve a dilution ratio of 60 times by weight of the cellulose ether, and the resulting dilution was stirred for a certain period of time to prepare an aqueous solution in which the solid content concentration of cellulose ether (1) was 1.0% by weight. [Example 2] An aqueous solution of cellulose ether (2) with a solid content concentration of 1.0% by weight was prepared in the same manner as in Example 1, except that cellulose ether (2) was used instead of cellulose ether (1). [Example 3] Boiling water was added to the cellulose ether (2) above to a dilution ratio of 8 times by weight of the cellulose ether, and the resulting dilution was stirred for a certain period of time. After stirring, room temperature water was added to the diluted solution to a dilution ratio of 12 times by weight of the cellulose ether, and the resulting dilution was stirred for a certain period of time to prepare an aqueous solution in which the solid content concentration of cellulose ether (2) was 5.0% by weight. [Comparative Example 1] After adding water to the starch paste mentioned above, the mixture was heated to over 90°C to dissolve and gelatinize the starch paste, preparing an aqueous solution with a solid content concentration of 2.0% by weight of the starch paste.

[0055] (2) Apparatus and reagents For sizing (adhesive application), we prepared a mini-sizing machine DCI001P (manufactured by Kaji Seisakusho Co., Ltd.) and an HGA-357 adhesive application machine (manufactured in China, with an adhesive tank capacity of approximately 47L).

[0056] (3) Operating Procedure [Example 1] 2500 ml of the aqueous solution of cellulose ether obtained in Example 1 above (1) was added to the aforementioned gluing machine: Mini Sizer DCI001P. Furthermore, cotton yarn (1) manufactured by Izawa Towel Co., Ltd. (raw silk (unprocessed yarn, spun yarn, etc.), 100% cotton, 20 count, single yarn, twist coefficient 4.5, average fiber length approximately 25 mm), fed from a cheese bobbin, was placed into the aqueous solution of cellulose ether in the sizing machine. At this time, the weight of the cotton yarn (1) per unit length fed from the cheese bobbin was measured. Subsequently, the cotton yarn coated with sizing solution (aqueous solution) was passed through a squeezing roll (first passing roll) under a pressure load of 0.04 MPa and an immersion roll (second passing roll) under a pressure load of 0.06 MPa. Furthermore, the yarn was passed through a hot air drying section with a temperature of 110°C and a drying chamber length of approximately 3.8 m, and a cylinder roll drying section with a temperature of 110°C and seven cylinders with a diameter of 100 mm each, at a speed of 10 m / min to perform the sizing treatment. The weight of the cotton yarn (1) per unit length was measured for the dried (sizing) cotton yarn (1) obtained.

[0057] [Comparative Example 1] 35 L of the aqueous solution of the starch paste obtained in Comparative Example 1 in (1) above was poured into the aforementioned adhesive machine: HGA-357 type adhesive machine. Furthermore, cotton yarn (1) manufactured by Izawa Towel Co., Ltd. (raw silk (unprocessed yarn, spun yarn, etc.), 100% cotton, 20 count, single yarn, twist coefficient 4.5, average fiber length approximately 25 mm), fed from a cheese bobbin, was placed into the above-mentioned starch paste aqueous solution in a sizing machine. At this time, the weight of cotton yarn (1) per unit length fed from the cheese bobbin was measured. Subsequently, the cotton yarn with the paste solution (aqueous solution) attached was passed through a drying chamber of approximately 20 m and dried at 300°C. Then, excess paste was removed using a cylinder roll at approximately 120°C, and the resulting sizing-treated cotton yarn (1) was wound onto a weaving beam. The passage speed of the cotton yarn in the drying chamber and cylinder roll was set to 30 m / min. The weight of cotton yarn (1) per unit length was measured for the resulting dried (sizing-treated) cotton yarn (1).

[0058] [Examples 2 and 3] 2500 ml of aqueous solutions of each cellulose ether obtained in Examples 2 and 3 above were added to the aforementioned gluing machine: Mini Sizer DCI001P. Furthermore, cotton yarn (2) manufactured by Izawa Towel Co., Ltd. (raw silk, 20 count, single yarn, made from long-staple cotton, combed, with fewer short fibers and less fluff compared to cotton yarn (1) above) was fed from a cheese bobbin and placed into each of the cellulose ether aqueous solutions in the sizing machine. At this time, the weight of cotton yarn (2) per unit length fed from the cheese bobbin was measured. After that, sizing treatment was performed in the same manner as the sizing treatment of cotton yarn in Example 1 above. The weight of cotton yarn (2) per unit length was measured for the obtained dried (after sizing) cotton yarn (2).

[0059] (4) Evaluation (4-1) Viscosity of aqueous solution containing a binder The viscosity (mPa·s) of the aqueous solutions of cellulose ether from Examples 1 and 3 obtained in (1) above, and the aqueous solution of starch paste from Comparative Example 1, was measured at 20°C using a BL-type viscometer (manufactured by Tokimec Co., Ltd.). (4-2) Adhesion rate (amount of adhesive) For each sizing yarn of Examples 1 to 3 and Comparative Example 1, the sizing rate (S) was calculated based on the following formula (1), using the weight of the cotton yarn before sizing (g) (weight before treatment) and the weight of the cotton yarn after sizing (g) (weight after treatment) as described in (3) above.

[0060]

number

[0061] (4-3) Wear strength (number of friction cycles) For each of the glued yarns in Examples 1-3 and Comparative Example 1, the abrasion strength was measured using a yarn stringing test machine (1065, manufactured by Maeda Seisakusho) in accordance with JIS L 1095:2010 (9.10 Abrasion strength Method B). Specifically, abrasion tests were conducted under the following test conditions, and the number of friction cycles until two out of 20 sample yarns broke was measured. <Test Conditions> ·Friction speed: 120 times / min ·Friction angle: 110 degrees ·Round distance: 2.5cm • Test length: 20cm • Friction element: 0.6 mm diameter hard steel wire

[0062] (4-4) Tensile strength and elongation of single yarn For each of the glued yarns in Examples 1-3 and Comparative Example 1, the tensile strength and elongation of the single yarn were measured using a tensile testing machine (Autograph AG-Xplus, manufactured by Shimadzu Corporation) under the conditions of a gripping distance of 20 cm and a tensile speed of 20 cm / min, in accordance with JIS L 1095:2010 (9.5 Tensile strength and elongation of single yarns).

[0063] (4-5) Observation using a scanning electron microscope Using a desktop microscope (Miniscope® TM4000Plus, manufactured by Hitachi High-Technologies Corporation), the surfaces of the cotton yarn before sizing and the cotton yarn after sizing in Example 1 were observed at an acceleration voltage of 15kV. In addition, using a super-depth multi-angle lens VHX-D510 (SEM 200x, manufactured by Keyence Corporation), the surface of the cotton yarn after sizing in Comparative Example 1 was observed at an acceleration voltage of 0.9kV.

[0064] Table 1 shows the evaluation results for Example 1 and Comparative Example 1 as described in (4-1) to (4-4) above, and Table 2 shows the evaluation results for Examples 2 and 3 as described in (4-1) to (4-4) above. Furthermore, the SEM observation results for Example 1 and Comparative Example 1 described in (4-5) above are shown in Figures 2 to 4. Figure 2 is an SEM image (magnification: 150x) of cotton yarn without adhesive, Figure 3 is an SEM image (magnification: 200x) of cotton yarn with starch adhesive attached (Comparative Example 1), and Figure 4 is an SEM image (magnification: 150x) of cotton yarn with cellulose ether (1) attached (Example 1).

[0065] [Table 1]

[0066] [Table 2]

[0067] As shown in Table 1, the aqueous solution containing cellulose ether (1) in Example 1 had a higher viscosity and more appropriate viscosity compared to the aqueous solution containing starch paste in Comparative Example 1. Having appropriate viscosity allows for good penetration, suppresses overall fluffing, and exhibits good convergence. Therefore, from these results, it was found that the aqueous solution containing cellulose ether (1) is optimal as a sizing agent from the viewpoint of efficiency during weaving.

[0068] Furthermore, as shown in Table 1, the cotton yarn with cellulose ether (1) attached in Example 1 was found to have approximately 120% more friction cycles and superior abrasion resistance compared to the cotton yarn with starch paste attached in Comparative Example 1. In addition, although the single-ply tensile strength of the cotton yarn in Example 1 was approximately 3% lower than that of the cotton yarn in Comparative Example 1, it could be considered equivalent and was at a level that was practically acceptable for cotton yarn with a sizing agent. Moreover, the cotton yarn in Example 1 was found to have approximately 20% higher elongation than the cotton yarn in Comparative Example 1, demonstrating superior elongation. As shown in Table 1, the adhesion rate of the sizing agent (cellulose ether (1)) to the cotton yarn of Example 1 was approximately half that of the adhesion rate of the sizing agent (starch paste) to the cotton yarn of Comparative Example 1. Despite this low adhesion rate of the sizing agent, it was found that the cotton yarn of Example 1 exhibited physical properties equivalent to or better than those of the cotton yarn of Comparative Example 1, as described above. From these results, it was found that by using the cellulose ether of the present invention as a sizing agent, it is possible to impart excellent physical properties to cotton yarn while reducing the amount of sizing agent used, thereby suppressing costs and environmental impact.

[0069] Furthermore, as mentioned above, starch pastes like the one used in Comparative Example 1 require the addition of components other than cornstarch, the main component of starch, such as wax, propylene glycol, and polyvinyl alcohol (PVA), to improve the convergence, smoothness, and flexibility of the fibers, which leads to increased complexity of formulation and higher costs. On the other hand, the results in Table 1 show that the cellulose ether (1) in Example 1 can improve the convergence, smoothness, and flexibility of the fibers even when the adhesive consists solely of cellulose ether (1) without the addition of any other components, demonstrating properties not found in conventional starch pastes.

[0070] Furthermore, the SEM image in Figure 4 shows that when cellulose ether (1) was used as the adhesive, fluffing was suppressed and the material was fixed overall with the adhesive. On the other hand, the SEM image in Figure 3 shows that when starch paste was used as the adhesive, fluffing was not completely suppressed, and the convergence was inferior compared to the case of cellulose ether (1). From the results in Table 1 and Figures 2-4 above, it was found that the cellulose ether of the present invention has low viscosity, good impregnation properties, and excellent convergence even when the adhesion rate of the adhesive is low.

[0071] Furthermore, the results in Table 2 show that aqueous solutions containing cellulose ether (2) can be used as adhesives. The results in Tables 1 and 2 show that cellulose ether (A) of the present invention is useful as an adhesive regardless of its type.

[0072] 2. Evaluation of the weaving properties of textile products treated with sizing agents. Furthermore, as shown in 1. above, since the cotton yarn of Example 1 exhibits physical properties equivalent to or better than those of the cotton yarn of Comparative Example 1, it can be estimated that the weaving speed on an air jet loom is equivalent (approximately 350-400 rpm) for both the cotton yarn of Example 1 and the cotton yarn of Comparative Example 1. As a result, it can be estimated that the daily (8-hour) production volume of towels, which are the woven fabric, is also equivalent (approximately 30-50 kg) for both the cotton yarn of Example 1 and the cotton yarn of Comparative Example 1. As also mentioned in the analysis results of the SEM images above, the cotton yarn of Example 1, in which fluffing is almost suppressed, is less likely to pill during weaving and there is less concern about yarn breakage compared to the cotton yarn of Comparative Example 1, in which fluffing occurs. From the above, it has been found that by using the cellulose ether of the present invention as a sizing agent, the amount of sizing agent used can be reduced, thereby suppressing costs and environmental impact while maintaining the production efficiency of textiles.

[0073] 3. Environmental evaluation of the gluing process As in Comparative Example 1, if starch paste is used and the adhesion rate is set to 3% by weight, and 450 kg of cotton yarn (20 count, single yarn) is to be sizing, it is assumed that the sizing machine needs to be operated under the following conditions: water usage: 675 L, processing time: 1 hour, processing temperature: 95~120°C. In this case, assuming that the output of the prime mover driving the gluing machine is 8 kW, the electricity cost is 23 yen / kWh, and the CO2 emission factor is 0.47 kg / kWh, the power consumption can be calculated as 8 (kW) × 1 (hour) = 8 (kWh). As a result, the electricity cost required for operating the gluing machine is 23 (yen / kWh) × 8 (kWh) = 184 (yen), and the CO2 emission amount during the operation of the gluing machine is 0.47 (kg / kWh) × 8 (kWh) = 4 (kg). Also, it is assumed that 608 kg of steam is required to raise the temperature to 95 - 120 °C. Further, since the amount of heat required to apply pressure to water at 20 °C to make steam is assumed to be 2607 kJ / kg, the amount of heat required for heating can be roughly estimated as 608 (kg) × 2607 (kJ / kg) × 1 / 1000 = 1584 (MJ). When raising the temperature of the steam using city gas, the lower calorific value of city gas: 40.3 MJ / m 3 , CO2 emission factor: 2.23 kg / m 3 , fuel cost: 100 yen / m 3 , boiler efficiency: 0.9, then the amount of city gas used: 1584 (MJ) ÷ 0.9 ÷ 40.3 (MJ / m 3 ) = 44 (m 3 ) can be calculated. As a result, the city gas cost required for heating is 44 (m 3 ) × 100 (yen / m 3 ) = 4400 (yen), and the CO2 emission amount during heating is 44 (m 3 ) × 2.23 (kg / m 3 ) = 97 (kg) can be calculated.

[0074] Starch paste like Comparative Example 1 is insoluble in water at normal temperature (20 °C) and needs to be heated to about 90 °C to dissolve and gelatinize, so the above-mentioned operation of heating with steam is required. On the other hand, the cellulose ether of the present invention has the property of being poorly soluble in high-temperature liquids such as hot water, and readily soluble in low-temperature liquids such as cold water and room-temperature water. Therefore, when methylcellulose is used as a binder as in Example 1, bonding at room temperature (20°C) is preferable, and the above-mentioned steam heating process becomes unnecessary. Consequently, in the case of Example 1, the above-mentioned city gas cost of 4,400 yen and CO2 emissions of 97 kg associated with the heating process are eliminated, reducing energy consumption and CO2 emissions, and thus reducing the environmental burden.

[0075] 4. Measurement of BOD and COD of aqueous solutions containing adhesives Using the cellulose ether (1) described in 1.(1) above, an aqueous solution of cellulose ether (1) with a solid content concentration of 1.0% by weight was prepared according to the same procedure as in 1.(1) above. In addition, using the starch paste described in 1.(1) above, water was added to the starch paste, and then heated to 90°C or higher to dissolve and gelatinize the starch paste, thereby preparing an aqueous solution of starch paste with a solid content concentration of 1.0% by weight. For aqueous solutions of methylcellulose or starch paste, the BOD (biochemical oxygen content) and COD (chemical oxygen content) were measured based on JIS K 0102:2016 (21. Biochemical oxygen consumption (BOD)) and (17. Oxygen consumption by potassium permanganate at 100°C (COD)). The results are shown in Table 3. BOD (Biochemical Oxygen Demand) is a measure of how much oxygen is needed for microbial decomposition. COD (Chemical Oxygen Demand) is a measure of how much oxygen is needed when an oxidizing agent (potassium permanganate) is added to a substance. Both BOD and COD are used as indicators of water pollution, and the higher the value, the more polluting substances are present in the water.

[0076] [Table 3]

[0077] The results in Table 3 show that the BOD and COD of the aqueous solution of cellulose ether (1) were extremely low compared to the BOD and COD of the aqueous solution of starch paste, indicating that the cellulose ether of the present invention, as a pasteurizer, can suppress water pollution. As shown in Example 1 and Comparative Example 1 above, by using cellulose ether (1) as a sizing agent, it is possible to impart superior physical properties to cotton yarn even with a reduced amount compared to conventional starch sizing. In the tests shown in Table 3 above, the solid content concentrations of cellulose ether (1) and starch sizing were kept the same, but in actual sizing, the amount of cellulose ether (1) used can be reduced to further suppress water pollution during sizing.

[0078] 5. De-gluing using supercritical carbon dioxide (1) Fabric with sizing agent attached and cotton yarn with sizing agent attached (1-1) Fabric with cellulose ether (2) attached Boiling water was added to the cellulose ether (2) described above to a dilution ratio of approximately 14 times by weight of the cellulose ether, and the resulting dilution was stirred for a certain period of time. After stirring, room temperature water was added to the diluted solution to a dilution ratio of approximately 34 times by weight of the cellulose ether, and the resulting dilution was stirred for a certain period of time to prepare an aqueous solution in which the solid content concentration of cellulose ether (2) was 3.0% by weight. A 100% cotton fabric woven from raw silk manufactured by Izawa Towel Co., Ltd. was immersed in an aqueous solution of cellulose ether (2) obtained as described above, with a solid content concentration of 3.0% by weight. The immersed fabric was passed through the squeezing roll (first passing roll) and immersion roll (second passing roll) of the sizing machine: mini-sizer DCI001P shown in 1. (2) above, under a pressure load of 0.2 MPa, to remove excess sizing agent. The fabric was then dried in a dryer at 100-110°C for 30 minutes to prepare a fabric to which cellulose ether (2) had adhered (sizing agent adhesion rate calculated based on formula (1) in 1. (4-2) above: 3.24%).

[0079] (1-2) Fabric with cellulose ether (3) attached Cellulose ether (3): Metholose (registered trademark) 60SH-50 (hydroxypropyl methylcellulose, weight-average molecular weight: 80000, degree of methoxy group substitution: 1.9, number of hydroxypropoxy group substitution moles: 0.25, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared, and boiling water was added to the cellulose ether (3) to a dilution ratio of approximately 20 times by weight of the cellulose ether, and the resulting dilution was stirred for a certain period of time. After stirring, room temperature water was added to the diluted solution to a dilution ratio of approximately 30 times by weight of the cellulose ether, and the resulting dilution was stirred for a certain period of time to prepare an aqueous solution in which the solid content concentration of cellulose ether (3) was 2.0% by weight. A 100% cotton fabric woven from raw silk manufactured by Izawa Towel Co., Ltd. was immersed in an aqueous solution of cellulose ether (3) obtained as described above, with a solid content concentration of 2.0% by weight. The immersed fabric was passed through the squeezing roll (first passing roll) and immersion roll (second passing roll) of the sizing machine: mini-sizer DCI001P shown in 1. (2) above, under a pressure load of 0.2 MPa, to remove excess sizing agent. The fabric was then dried in a dryer at 100-110°C for 30 minutes to prepare a fabric with cellulose ether (3) attached (sizing agent attachment rate calculated based on formula (1) in 1. (4-2) above: 1.69%).

[0080] (1-3) Cotton yarn coated with cellulose ether (3) Furthermore, 2500 ml of an aqueous solution of cellulose ether (3) obtained in (1-2) above, with a solid content concentration of ○% by weight, was placed into the sizing machine: Mini Sizer DCI001P shown in (2) above. Then, cotton yarn (1) (raw silk (unprocessed yarn, spun yarn, etc.), 100% cotton, 20 count, single yarn, twist coefficient 4.5, average fiber length approximately 25 mm) manufactured by Izawa Towel Co., Ltd. was processed in the same manner as the sizing method described in [Example 1] in (3) above to prepare cotton yarn to which cellulose ether (3) was attached (sizing rate calculated based on formula (1) in (4-2) above: 1.6%).

[0081] (2) Apparatus and reagents Figure 5 shows an overview of the entire apparatus used in the treatment with a fluid containing supercritical carbon dioxide. In Figure 5, each symbol indicates the following: 1: chiller unit, 2: CO2 supply pump, 3: air release valve, 4: check valve, 5: pressure transmitter, 6: safety valve, 7: staining container, 8: container drain valve, 9: container temperature sensor, 10: magnetic induction agitator, 11: exhaust flow control valve, 12: container exhaust valve, 13: control panel, 14: outlet for CO2 supply pump, 15: outlet for staining container heating heater, and A: CO2 cylinder. A cooling water circulation device LTC-450α (manufactured by AS ONE Corporation) was used as chiller unit 1, a double plunger pump NP-KX-500 (manufactured by Nippon Precision Science Co., Ltd.) was used as CO2 supply pump 2, and a high-pressure vessel (manufactured by ITEC Corporation, model: C-04-M-FU, capacity: 400 ml) was used as staining container 7. The carbon dioxide supply source used was liquefied carbon dioxide cylinders (Kind Gas Co., Ltd., purity 99.5% or higher).

[0082] (3) Operating Procedure (3-1) Fabric with cellulose ether (2) attached A jig (110 cm long x 15 mm outer diameter, hollow cylindrical, mesh structure, made of metal) was prepared, and a piece of fabric (approximately 10 cm x 10 cm, approximately 2 g) coated with the cellulose ether (2) described in (1-1) above was wrapped around the jig. Cotton string was further wrapped around the jig to secure the fabric and prevent it from coming off. Figure 6(a) shows the jig with the fabric wrapped around it. Furthermore, an outer cylinder (110 cm long, 36 mm inner diameter, 41 mm outer diameter, hollow cylindrical) was prepared, and a paper wiper (Kimwipes®, 120 mm x 210 mm) that had been evenly soaked with 1 ml of water, the cosolvent, was wrapped around the outside of the outer cylinder. Cotton string was then wrapped around it to secure the wrapped paper wiper and prevent it from coming off. Figure 6(b) shows the outer cylinder with the paper wiper wrapped around it. The jig wrapped with the above-mentioned fabric was placed and fixed inside the outer cylinder wrapped with a paper wiper to obtain a sample for measurement. The obtained sample for measurement was placed in the staining container 7. Next, 200 ml of carbon dioxide was supplied to the staining container 7 using the CO2 supply pump 2 at a flow rate of 20-300 ml / min, pressurizing the inside of the staining container 7. The conditions for treating the sample for measurement with supercritical carbon dioxide fluid were 40°C, 10 MPa, 120 minutes, and in batch mode. A propeller was used for stirring, with one set consisting of 60 seconds of forward rotation and 60 seconds of reverse rotation, and this set was repeated for 120 minutes at 900 rpm. The water soaked into the paper wiper became mixed with supercritical carbon dioxide, and the volume ratio of supercritical carbon dioxide to water was 200:1. After treatment with supercritical carbon dioxide fluid, the valve of the staining container 7 was opened and the pressure was released to atmospheric pressure. After releasing the pressure from the dyeing container 7, the fabric was removed from the jig and dried at 105°C for 2 hours, and the dried fabric was weighed.

[0083] (3-2) Fabric with cellulose ether (3) attached A jig similar to the one used in the process described in (3-1) above was prepared, and a piece of fabric (approximately 10 cm x 10 cm, approximately 8 g) coated with the cellulose ether (3) described in (1-2) above was wrapped around the jig. Cotton string was then wrapped around the jig to secure the fabric and prevent it from coming off. The jig with the fabric wrapped around it was in the same state as shown in Figure 6(a). Furthermore, an outer cylinder similar to the one used in the process described in (3-1) above was prepared, and a paper wiper (Kimwipes®, 120mm x 210mm) soaked evenly with 5ml of EGME (ethylene glycol monobutyl ether), the cosolvent, was wrapped around the outside of the outer cylinder. Cotton string was then wrapped around it to secure the wrapped paper wiper and prevent it from coming off. The outer cylinder with the paper wiper wrapped around it was in the same state as in Figure 6(b). The jig, to which the above-mentioned fabric was wrapped, was placed and fixed inside the outer cylinder to which a paper wiper was wrapped, and a sample was obtained for measurement. The obtained sample was placed in the dyeing container 7, and the sample was treated with supercritical carbon dioxide fluid in the same manner as in (3-1) above, except that the conditions for treating the sample with supercritical carbon dioxide fluid were changed from 40°C, 10 MPa, time 120 minutes, batch type to 120°C, 25 MPa, time 180 minutes, batch type. The EGME soaked into the paper wiper became mixed with supercritical carbon dioxide, resulting in a volume ratio of supercritical carbon dioxide:fabric of 45:1 and a volume ratio of supercritical carbon dioxide:EGME of 80:1. After treatment with supercritical carbon dioxide fluid, the valve of the dyeing container 7 was opened and the pressure was released to atmospheric pressure. After releasing the pressure from the dyeing container 7, the fabric was removed from the jig and dried at 100°C for 1 hour, and the dried fabric was weighed.

[0084] (3-3) Cotton yarn coated with cellulose ether (3) A jig similar to the one used in the process described in (3-1) above was prepared, and cotton thread (length: approximately 400m, approximately 10g) coated with cellulose ether (3) as described in (1-3) above was wrapped around the jig. Cotton string was then wrapped around the jig to secure it and prevent it from coming off. Figure 7 shows the jig with the cotton thread wrapped around it. Furthermore, an outer cylinder similar to the one used in the process described in (3-1) above was prepared, and a paper wiper (Kimwipes®, 120mm x 210mm) soaked evenly with 5ml of EGME (ethylene glycol monobutyl ether), the cosolvent, was wrapped around the outside of the outer cylinder. Cotton string was then wrapped around it to secure the wrapped paper wiper and prevent it from coming off. The outer cylinder with the paper wiper wrapped around it was in the same state as in Figure 6(b). The jig with the cotton yarn wrapped around it was placed and fixed inside the outer cylinder with a paper wiper wrapped around it to obtain a sample for measurement. The obtained sample for measurement was placed in the staining container 7 and treated with supercritical carbon dioxide fluid in the same manner as in (3-2) above. The EGME soaked into the paper wiper was mixed with supercritical carbon dioxide, resulting in a volume ratio of supercritical carbon dioxide to cotton yarn of 40:1 and a volume ratio of supercritical carbon dioxide to EGME of 80:1. After treatment with supercritical carbon dioxide fluid, the valve in the staining container 7 was opened and the pressure was released to atmospheric pressure. After releasing the pressure in the staining container 7, the cotton yarn was removed from the jig and dried at 110°C for 1 hour, and the dried cotton yarn was weighed.

[0085] (4) Evaluation (4-1) Removal rate of adhesive First, using the weight (g) of the fabric or cotton yarn before the sizing and desizing treatments, and the weight (g) of the fabric or cotton yarn after the desizing treatment, the adhesion rates of cellulose ether (2) or cellulose ether (3) (sizing agent) to the fabric or cotton yarn after the desizing treatment were calculated based on the formula (1) described in 1. (4-2) above. Then, using the sizing agent adhesion rate (%) of the sizing agent on the sizing-treated fabric or cotton yarn (fabric or cotton yarn after sizing treatment and before desizing treatment) (3.24%, 1.69%, or 1.6% as described above) and the sizing agent adhesion rate (%) of the fabric or cotton yarn after desizing treatment, the desizing rate (Desizing rate D) was calculated based on the following formula (2).

[0086]

number

[0087] Regarding the fabric, the calculated removal rate of cellulose ether(2) (sizing agent) was approximately 12%. From this result, it was found that cellulose ether(2) can be removed by desizing treatment with supercritical carbon dioxide. It is presumed that the removal rate of the sizing agent can be further increased through improvements such as improving stirring efficiency and increasing the number of batches. Furthermore, when the solubility of cellulose ether(2) (thickener) in supercritical carbon dioxide fluid (total of supercritical carbon dioxide and water) was calculated (amount of dissolved cellulose ether(2) (thickener) (g) / volume of supercritical carbon dioxide fluid (ml)), it was found to be 3.7 × 10⁻⁶. -5 The concentration was g / ml.

[0088] Regarding the fabric, the calculated removal rate of the obtained cellulose ether(3) (sizing agent) was approximately 98%. From this result, it was found that cellulose ether(3) can be removed with an extremely high removal rate by desizing treatment using supercritical carbon dioxide with EGME as a cosolvent. Furthermore, when the amount of EGME added was increased and the de-sticking treatment was performed in the same manner, it was found that the removal rate of cellulose ether (3) (sticking agent) improved even when the ratio of the volume of supercritical carbon dioxide to the volume of EGME (volume of supercritical carbon dioxide / volume of EGME) was lowered. Furthermore, when the solubility of cellulose ether (3) (thickener) in supercritical carbon dioxide fluid (total of supercritical carbon dioxide and EGME) was calculated (amount of dissolved cellulose ether (3) (thickener) (g) / volume of supercritical carbon dioxide fluid (ml)), it was found to be 3.1 × 10⁻⁶. -3 The concentration was g / ml.

[0089] Regarding cotton yarn, the calculated removal rate of the obtained cellulose ether(3) (sizing agent) was approximately 96%. Furthermore, the solubility of cellulose ether(3) (sizing agent) in supercritical carbon dioxide fluid (total of supercritical carbon dioxide and EGME) was calculated as (amount of dissolved cellulose ether(3) (sizing agent) (g) / volume of supercritical carbon dioxide fluid (ml)), and it was found to be 3.5 × 10⁻⁶. -3 The concentration was g / ml. By comparing the results for these cotton yarns with the results for cellulose ether(3) (sizing agent) in the aforementioned fabrics, it was found that there was no change in the removal rate and solubility of cellulose ether(3) (sizing agent) regardless of whether fabric or cotton yarn was used as the target for desizing, indicating that cellulose ether(3) can be removed very efficiently.

[0090] (4-2) Observation using a scanning electron microscope Using a desktop microscope (Miniscope® TM4000Plus, manufactured by Hitachi High-Technologies Corporation), the surfaces of the fabric to which the cellulose ether (3) described in (3-2) above had adhered were observed at an acceleration voltage of 15kV, both before the desizing treatment with the adhesive adhering to the fabric and after the desizing treatment. The SEM observation results are shown in Figures 8 and 9. Figure 8 is an SEM image (magnification: 200x) of the fabric with the sizing agent attached before the desizing treatment, and Figure 9 is an SEM image (magnification: 200x) of the fabric after the desizing treatment. A comparison of Figures 8 and 9 reveals that before the desizing treatment (Figure 8), the threads were converged due to the sizing agent, but after the desizing treatment (Figure 9), the threads constituting the fabric spread out, resulting in weaker convergence.

[0091] (4-3) Water-wetting properties (water absorption) For the fabrics to which the cellulose ether (3) described in (3-2) above was attached, the water wettability (water absorption) of the fabrics with the sizing agent attached before the desizing treatment and the fabrics after the desizing treatment were evaluated. The water wettability of the fabric was measured according to the drop method specified in "JIS L 1907 Test Method for Water Absorption of Textile Products". Figure 10 shows photographs of the fabric after water wettability evaluation. The fabric on the left in Figure 10 is the fabric with the sizing agent still attached before the desizing treatment, and the fabric on the right in Figure 10 is the fabric after the desizing treatment. As can be seen in Figure 10, in the fabric with the sizing agent still attached before the desizing treatment, water droplets remained on the surface of the fabric, and almost no water absorption was observed. On the other hand, in the fabric after the desizing treatment, water was absorbed from the surface of the fabric, and no water droplets were present on the surface. These results indicate that the cellulose ether sizing agent is sufficiently removed by the desizing treatment with supercritical carbon dioxide, allowing the fabric to exhibit its water absorption properties.

[0092] From the above, it has been found that the sizing agent-coated textile product of the present invention exhibits excellent fiber convergence properties. Furthermore, the following points were confirmed from the results above. The sizing-coated textile product of this embodiment can improve the convergence of fibers without excessively increasing the amount of sizing applied, or it can exhibit high tensile strength, or it can have high durability against friction, and the tensile strength does not decrease easily even after friction testing. The adhesive of this embodiment can keep the BOD and / or COD values ​​in solution lower than conventional starch pastes, thereby suppressing water pollution. The method for producing textile products from sizing-coated textile products according to this embodiment allows for efficient removal of the sizing agent, resulting in textile products with excellent water wettability. [Explanation of Symbols]

[0093] 1: Chiller unit 2: CO2 supply pump 3: Air release valve 4: Check valve 5: Pressure Transmitter 6: Safety valve 7: Dyeing container 8: Container drain valve 9: Container temperature sensor 10: Magnetic induction type stirrer 11: Exhaust flow control valve 12: Container exhaust valve 13: Control Panel 14: Outlet for CO2 supply pump 15: Outlet for heating element of staining container A: CO2 cylinder

Claims

1. A method for producing a textile product from a textile product coated with a sizing agent, The process includes a step of removing the starch from the starched textile by bringing a fluid containing supercritical carbon dioxide into contact with the starched textile, Here, the sizing-coated textile product is a sizing-coated textile product manufactured by a method that includes the step of applying sizing to the textile product by bringing a fluid containing the sizing agent into contact with the textile product under temperature conditions in the range of 0 to 55°C. The adhesive comprises at least one cellulose ether (A) selected from the group consisting of methylcellulose, hydroxypropyl methylcellulose, and hydroxyethyl methylcellulose. The content of the cellulose ether (A) in the adhesive is 80% by weight or more and 100% by weight or less. The aforementioned textile product is a fabric (excluding nonwoven fabrics that are composed of fibers and are hydrolyzable), The method wherein the type of fiber is at least one selected from the group consisting of plant fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, glass fibers, and metal fibers.

2. The method according to claim 1, wherein the step of removing the adhesive is performed by batch processing or continuous processing.

3. The method according to claim 1 or 2, wherein the temperature condition when the fluid containing the sizing agent is brought into contact with the textile product is in the range of 0 to 20°C.

4. The method according to claim 1 or 2, wherein the textile product includes a cotton fabric.

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