Fiber product with sizing agent, sizing agent, method for producing fiber product with sizing agent, and method for producing fiber product

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 textile product, a sizing agent, a method for producing a sizing textile product, and a method for producing a textile product. [Background technology]

[0002] Generally, woven fabrics such as cotton products are made by interlacing warp and weft threads. Therefore, the first step in making woven fabrics is to separate the raw yarns into warp and weft threads. The raw yarns separated into warp and weft threads are then put 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 product. The sizing agent used in the sizing process is required to perform various functions, such as increasing the convergence of the fibers, suppressing fiber fuzz, and imparting physical properties such as tensile strength and abrasion resistance to the fibers. Summary of the Invention [Problem to be solved by the invention]

[0003] As a sizing agent used in the sizing process, a sizing agent containing starch paste has been conventionally used. However, in order to improve the convergence, smoothness, flexibility, etc. of the fibers, a sizing agent containing starch paste needs to add ingredients such as wax, propylene glycol, polyvinyl alcohol (PVA) other than the main ingredient starch (corn starch, etc.), which leads to complexity of the blend and increased costs. Furthermore, as a result of intensive research by the present inventors, as shown in Comparative Example 1 described below, it was found that even when a starch paste containing ingredients other than the above starch is used as a sizing agent, there is still room for improvement in the convergence of the fibers. As described above, there is a demand for a fiber product with a sizing agent that has excellent fiber bundling properties.

[0004] An object of the present invention is to provide a sizing agent-coated textile product having excellent fiber bundling properties. [Means for solving the problem]

[0005] As a result of intensive research into solving the above problems, the inventors discovered that the above problems could be solved by using a sizing agent containing a specific cellulose ether, and thus completed the present invention. Specific embodiments of the present invention are as follows.

[0006] [1] A textile product with a sizing agent, The sizing agent comprises at least one cellulose ether (A) selected from the group consisting of alkyl cellulose, hydroxyalkyl cellulose, and hydroxyalkyl alkyl cellulose. [2] The sizing textile product according to [1], wherein the cellulose ether (A) comprises at least one selected from the group consisting of methyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose. [3] The sizing fiber product according to [1] or [2], wherein the substitution degree of the alkoxy group in the alkyl cellulose or the hydroxyalkyl alkyl cellulose is 1 to 3. [4] The sizing fiber product according to any one of [1] to [3], wherein the viscosity of the cellulose ether (A) when made into a 1 wt % or 5 wt % aqueous solution is 3 to 300 mPa·s. [5] The sizing textile product according to any one of [1] to [4], wherein the textile product comprises cotton yarn or cotton fabric. [6] The sizing textile product according to any one of [1] to [5], wherein the adhesion rate of the sizing agent to the sizing textile product is 0.1 to 10% by weight. [7] A sizing agent for producing a sizing-coated textile product according to any one of [1] to [6], comprising at least one cellulose ether (A) selected from the group consisting of alkyl cellulose, hydroxyalkyl cellulose, and hydroxyalkyl alkyl cellulose. [8] A method for producing a textile product with a sizing agent according to any one of [1] to [6], The method further comprises a step of contacting a textile product with a fluid containing the sizing agent to size the textile product. [9] A method for producing a textile product from the textile product with a sizing agent according to any one of [1] to [6], The method further comprises a step of contacting the sizing agent-coated textile product with a fluid containing supercritical carbon dioxide to desize the sizing agent-coated textile product.

[10] The method according to [9], wherein the desizing step is a batch process or a continuous process. Effect of the Invention

[0007] The fiber product with sizing agent of the present invention has excellent fiber bundling properties. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a temperature-pressure phase diagram of carbon dioxide. [Diagram 2] Figure 2 is an SEM image of cotton yarn with no sizing agent attached. [Diagram 3] Figure 3 is an SEM image of cotton yarn with starch sizing. [Figure 4] FIG. 4 is an SEM image of cotton yarn with cellulose ether (1) (methylcellulose) attached. [Diagram 5] FIG. 5 is a diagram showing an outline of an apparatus used for treatment with a fluid containing supercritical carbon dioxide. [Figure 6] Fig. 6(a) is a diagram showing the jig with the fabric wrapped around it, and Fig. 6(b) is a diagram showing the outer cylinder with the paper wiper wrapped around it. [Figure 7] FIG. 7 is a diagram showing the jig with cotton thread wound thereon. [Figure 8] Figure 8 is an SEM image of the fabric with cellulose ether (3) (hydroxypropyl methylcellulose) attached, with the sizing agent still attached before the desizing treatment. [Figure 9] FIG. 9 is an SEM image of the fabric with cellulose ether (3) (hydroxypropyl methylcellulose) attached after desizing treatment. [Figure 10] FIG. 10 is a photograph of the fabric after evaluation of water wettability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] In this specification, when a numerical range is expressed using "X to Y", the range is intended to include both ends of the range.

[0010] The sizing agent-coated textile product, the sizing agent, the method for producing the sizing agent-coated textile product, and the method for producing the textile product of the present invention will be described below.

[0011] 1. Textile products with sizing agent The sizing agent-coated textile product of the present invention is In the sizing textile product, the sizing agent 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 sizing agent of the present invention has excellent fiber bundling properties. In some cases, the textile product with a glue of this embodiment can improve the convergence of the fibers without excessively increasing the amount of glue attached, or the textile product with a glue of this embodiment can exhibit high tensile strength, or the textile product with a glue of this embodiment has high durability against friction and is less likely to experience a decrease in tensile strength even after a friction test.

[0012] (Adhesive) The sizing agent may further contain components other than the cellulose ether (A) or may not contain components other than the cellulose ether (A) (the sizing agent may be composed of the cellulose ether (A). In this specification, "not containing" a specific component means that the component is not intentionally added, and does not exclude the presence of the component as an impurity. The components other than the cellulose ether (A) 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 textile product of this embodiment, even when the sizing agent is composed of the cellulose ether (A) without adding any other components than the cellulose ether (A), the fiber convergence can be improved. As described above, in a sizing agent containing a conventional starch paste, it is necessary to add components other than starch to improve the convergence, smoothness, flexibility, etc. of the fiber, and the cellulose ether (A) has properties not found in conventional starch pastes. Since it is not necessary to add any components other than the cellulose ether (A), in the sizing textile product of this embodiment, the blending is not complicated, production efficiency is improved, and costs can be reduced.

[0013] The adhesion rate (amount of adhesion) of the sizing agent to the sizing agent-coated textile product 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 sizing agent is within the above range, pilling due to friction between threads or between threads and metal is less likely to occur, and thread breakage is reduced, improving weaving efficiency. The adhesion amount of the sizing agent to the sizing agent-coated textile product can be calculated based on the method and procedure described in (4-2) of 1. of [Examples] below.

[0014] The size (or the fluid containing the size) may be free of pigments, including, but not limited to, dyes, pigments, or mixtures thereof. The paste is not particularly limited, but may be a paste other than a printing paste (a paste for printing). Examples of such a paste other than a printing paste include a paste for warp threads of a textile.

[0015] (Cellulose Ether (A)) Alkyl cellulose is a type of cellulose ether, and can be produced by reacting cellulose with an etherifying agent. Alkyl cellulose is a compound in which some or all of the hydrogen atoms in the hydroxyl groups (-OH) of cellulose are replaced with alkyl groups (-R), converting them into alkoxy groups (-OR). Unalkylated cellulose is insoluble in water, but when it is alkylated to reduce the number of hydroxyl groups, the hydrogen bonds between the hydroxyl groups are weakened, making it water-soluble. The alkyl cellulose is not particularly limited, but may include or consist of methyl cellulose, ethyl cellulose, or a combination thereof. Among these, methyl cellulose is preferred, and the use of methyl cellulose allows sizing in an aqueous system, reduces costs, and facilitates desizing with supercritical carbon dioxide, which will be described later.

[0016] Hydroxyalkyl cellulose is a compound in which some or all of the hydrogen atoms in the hydroxyl groups (-OH) of cellulose are replaced with hydroxyalkyl groups to convert them into hydroxyalkoxy groups. The hydroxyalkyl cellulose can include or consist of, but is not limited to, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, or combinations thereof.

[0017] Hydroxyalkyl alkyl cellulose is a compound in which some or all of the hydrogen atoms in the hydroxyl groups (-OH) of cellulose are replaced with alkyl groups and hydroxyalkyl groups to convert them into alkoxy groups and hydroxyalkoxy groups. The hydroxyalkyl alkyl cellulose is not particularly limited, but may include or consist of hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, or a combination thereof. Among these, hydroxypropyl methyl cellulose is preferred, and the use of hydroxypropyl methyl cellulose makes it possible to perform sizing in an aqueous system, reducing costs, and facilitating desizing with supercritical carbon dioxide, which will be described later.

[0018] The cellulose ether (A) may include, but is not limited to, at least one selected from the group consisting of methyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose. One or a combination of two or more of these compounds may be used as the cellulose ether (A).

[0019] The degree of substitution of alkoxy groups in alkyl cellulose and / or hydroxyalkyl alkyl cellulose (average number of alkoxy groups present 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 adhesion amount of the sizing agent are both minimized, while the permeability into the yarn is good, leading to improved weaving efficiency. The degree of substitution of the alkoxy group may be the degree of substitution of a methoxy group. In the case of methylcellulose, the degree of substitution of the methoxy group is most preferably 1.64 to 1.92, and in the case of hydroxypropylmethylcellulose, the degree of substitution of the methoxy group is most preferably 1.79 to 2.04.

[0020] The molar substitution number of the hydroxyalkoxy group in the hydroxyalkyl cellulose and / or hydroxyalkyl alkyl cellulose 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 molar substitution number of the hydroxyalkoxy group is within the above numerical range, the concentration and adhesion amount of the sizing agent are both minimized, while the permeability into the yarn is good, leading to improved weaving efficiency. The molar substitution number of the hydroxypropoxy group is most preferably 0.18 to 0.34. In this specification, the number of moles of hydroxyalkoxy group substitution means the average number of moles of hydroxyalkoxy groups added per glucose ring unit of cellulose. The above-mentioned numerical range of the degree of substitution of methoxy groups and the above-mentioned numerical range of the number of moles of hydroxyalkoxy groups substituted can be combined arbitrarily.

[0021] The weight average molecular weight of the 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 the cellulose ether (A) is within the above numerical range, the concentration and adhesion amount of the sizing agent are both minimized, while the permeability into the yarn is good, leading to improved weaving efficiency. The weight average molecular weight of the cellulose ether (A) can be measured by the GPC method using a GPC apparatus (integrated apparatus, manufactured by Tosoh Corporation, HLC (registered trademark)-8420GPC) (column: SB-806MHQ 40°C, guard column: SB-G6B, both manufactured by Resonac Corporation) under the conditions of solvent, eluent: 0.1 M NaNO3 1.0 ml / min, injection volume: 100 μl.

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

[0023] The content of cellulose ether (A) in the paste can be 100% by weight (the paste is composed of cellulose ether (A)), in which case, as described above, the blending can be simplified to reduce costs while improving fiber convergence. The content of cellulose ether (A) in the paste can be 80% by weight or more, 90% by weight or more, or 95% by weight or more. The content of cellulose ether (A) in the paste can be 100% by weight or less. The above numerical ranges can be combined in any combination.

[0024] (Textiles) Examples of the textile product include, but are not limited to, fibers, threads, fabrics, etc. Examples of the fiber include tow before it becomes a thread, etc. Examples of the thread include, but are not limited to, spun yarn, filament yarn, mixed twisted yarn or mixed spun yarn obtained by mixing and twisting these, etc. Examples of the fabric include woven fabric or knitted fabric using the thread, nonwoven fabric, felt, etc. In this embodiment, it is preferable to use a thread as the textile product, and in this case, the thread to which the sizing agent obtained by the method is applied can be subjected to a subsequent weaving process. The textile article may also comprise or consist of cotton yarn or cotton fabric.

[0025] The type of yarn is not particularly limited, and examples of the yarn that can be used include natural fibers such as vegetable fibers such as cotton and hemp, 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, cupra, and lyocell, and chemical fibers such as inorganic fibers such as glass fibers, metal fibers, and carbon fibers. Two or more of these yarns may be mixed or twisted. These yarns may be single yarns, two-ply yarns, three-ply yarns, or four or more yarns twisted together. 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 may be the same as the type of yarn described above.

[0026] The sized textile product is not particularly limited, but may be a sized yarn or a sized fabric. The sizing yarn is not particularly limited, but may be used as a warp yarn for a woven fabric. The sizing fabric is not particularly limited, but may be a woven fabric including warp yarns sizing (with sizing agent attached) containing the cellulose ether (A) and weft yarns not sizing containing the cellulose ether (A). Here, the weft yarns not sizing containing the cellulose ether (A) mean weft yarns to which the sizing agent is not actively attached. Therefore, the weft yarns not sizing containing the cellulose ether (A) may include a case where the sizing warp yarns containing the cellulose ether (A) come into contact with the weft yarns, and the sizing agent of the warp yarns is transferred to the weft yarns.

[0027] 2. Adhesive The sizing agent of the present invention is a sizing agent for producing the sizing textile product described in 1 above, which contains at least one cellulose ether (A) selected from the group consisting of alkyl cellulose, hydroxyalkyl cellulose, and hydroxyalkyl alkyl cellulose. The starch paste of the present embodiment can reduce the BOD and / or COD values ​​when made into a solution, compared to conventional starch pastes, and can suppress water pollution. In the paste of this embodiment, the types and contents of the paste, cellulose ether (A), and fiber products can be the same as those described in 1 above.

[0028] As mentioned in 1 above, the paste (or the fluid containing the paste) may not contain a pigment. The paste may be a paste other than a printing paste (a paste for printing). Such a paste other than a printing paste may be a paste for warp threads of a textile.

[0029] 3. Method for producing sizing-applied textile products The method for producing a sizing-applied textile product of the present invention comprises the steps of: A method for producing a sizing agent-coated fiber product according to the above item 1, The method includes a step of contacting a textile product with a fluid containing the sizing agent to size the textile product.

[0030] In the method of this embodiment, the types, contents, and other components of the sizing agent, cellulose ether (A), and fiber products can be the same as those described in 1 above.

[0031] In this embodiment, the treatment conditions when the fluid containing the sizing agent is brought into contact with the textile product are not particularly limited, but from the viewpoint of improving sizing properties, 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. From the viewpoint of improving sizing properties, the pressure is preferably 0.01 to 0.2 MPa. Furthermore, from the viewpoint of improving sizing properties, the treatment time is preferably about 60 minutes per 450 kg of textile product. The step of contacting the textile with the fluid containing the sizing agent may be a batch process.

[0032] The amount of sizing agent used is not particularly limited, but for example, when cotton yarn is used as the textile product, it is preferable to use 0.03 to 0.07 g of sizing agent per 1 g of cotton yarn in order to improve sizing properties.

[0033] The content of the 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 the cellulose ether (A) in the fluid is within the above range, the concentration and adhesion amount of the sizing agent are both minimized, while the permeability into the yarn is good, leading to improved weaving efficiency.

[0034] In this embodiment, the fluid containing the adhesive may further contain, but is not limited to, a solvent. The solvent is not particularly limited, but may include or consist of water, glycol ether solvents, aqueous solvents such as 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, it is preferable to include water. When the fluid includes water, excellent solubility and appropriate viscosity can be obtained. The glycol ether solvent 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. Of these, it is preferable to include EGME. The lower alcohol may include or consist of, but is not limited to, methanol, ethanol, or combinations thereof. The content of the solvent in the fluid containing the paste 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 content of the solvent in the fluid containing the paste is within the above numerical range, the solubility of the solid content is improved.

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

[0036] When a solvent is used, the ratio (mol) of the solvent to 1 to 5 g of the paste is not particularly limited, but from the viewpoint of improving sizing properties, 1 to 6 mol is preferable.

[0037] The method of the present embodiment can be used as a sizing process, which is one of the fiber processing processes, and can also be used in combination with other fiber processing processes such as spinning, weaving, desizing, scouring, bleaching, dyeing, and finishing. The method of manufacturing a sizing-applied fiber product of the present embodiment can also be combined with a method of manufacturing a fiber product from a sizing-applied fiber product described below to form a single method or manufacturing method.

[0038] In the method of this embodiment, the step of sizing the textile product may include or consist of a step of contacting a fluid containing the sizing agent with a yarn to size the yarn. In this case, the method of this embodiment may further include a step of forming a fabric using the sizing agent-coated yarn to form a sizing fabric. In this case, the method of this embodiment may further include a step of forming a sizing fabric using the sizing agent-coated yarn as a warp yarn to form a woven fabric to form a sizing fabric.

[0039] 4. Method for producing textile products from textile products with sizing agent The method for producing a textile product from a sizing agent-coated textile product of the present invention includes the steps of: A method for producing a textile product from the sizing-applied textile product described in 1 above, comprising the steps of: The method includes a step of contacting the sizing agent-coated textile product with a fluid containing supercritical carbon dioxide to desize the sizing agent-coated textile product. The method for producing textile products from textile products with sizing agent of the present embodiment can efficiently remove the sizing agent, and can provide textile products with excellent water wettability.

[0040] In the method of this embodiment, the types, contents, and other components of the sizing agent, cellulose ether (A), and fiber products can be the same as 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 the product obtained by the method for producing a sizing agent-coated textile product described in 3 above can be used.

[0042] Here, supercritical carbon dioxide will be described. It is known that supercritical carbon dioxide is used for textile processing. The supercritical state occurs when the temperature (Tc) and pressure (Tp) of each compound are exceeded. This state is called a supercritical fluid and has properties between a gas and a liquid. As shown in Figure 1, the Tc of carbon dioxide is 31.1°C and the Tp is 7.38MPa, which are relatively mild conditions that allow the supercritical state to be expressed. It has the advantages of being non-explosive, non-toxic, highly safe, inexpensive, and easy to obtain. In addition, supercritical carbon dioxide has the following characteristics: (1) When the pressure is slightly changed near the critical temperature, the density fluctuates greatly; (2) It has excellent transport properties and high penetration into materials due to its low viscosity and high diffusivity; (3) It has high thermal conductivity and high heat transfer rate; (4) It has a high reaction rate due to the solvation effect; (5) It has a smaller dielectric constant than water and is comparable 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 carbon dioxide.

[0043] In this embodiment, the treatment conditions when the fluid containing supercritical carbon dioxide is brought into contact with the textile product with a sizing agent are not particularly limited, but from the viewpoint of improving the desizing property, the temperature can be 31 to 150°C or 40 to 120°C, the pressure can be 8 to 25 MPa or 10 to 25 MPa, and the time can be 30 to 800 minutes or 120 to 180 minutes. In this embodiment, the desizing step can be a batch process or a continuous process.

[0044] In this embodiment, the fluid containing supercritical carbon dioxide may further contain a co-solvent, which can improve the solubility of the sizing agent in the solvent (containing supercritical carbon dioxide and the co-solvent) and thereby improve the removability of the sizing agent. The co-solvent is not particularly limited, and the solvents described in 3 above can be used, but it is preferable to use a glycol ether solvent, especially EGME. By using the solvents described in 3 above as the co-solvent, the solubility of the sizing agent in the solvent (including supercritical carbon dioxide and the co-solvent) can be improved, thereby improving the removability of the sizing agent. The above effect is particularly remarkable when EGME is used as the co-solvent.

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

[0046] In this embodiment, when the desizing process is a batch process and a co-solvent is used, the ratio (mol %) of the co-solvent to the supercritical carbon dioxide is not particularly limited, but from the viewpoint of improving the solubility of the sizing agent in the solvent and improving the desizing properties, a ratio of 0.1 to 2 mol % is preferable. The volume ratio of supercritical carbon dioxide to the 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 the 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 step is a continuous process, the flow rate of supercritical carbon dioxide into the processing vessel is not particularly limited, but from the viewpoint of improving the solubility of the sizing agent in the solvent and improving the desizing properties, it is preferably 50 ml to 2000 ml, and more preferably 100 ml to 1500 ml per 1 g of fiber.

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

[0049] The removal rate (%) of the sizing agent after desizing by the method of this embodiment is not particularly limited, but may be 1 to 99%, etc. The removal rate (%) of the sizing agent can be calculated based on the procedure and method described in (4-1) of 5. of [Examples] described later. In the method of the present embodiment, the solubility of the paste in the fluid containing supercritical carbon dioxide (amount of the paste dissolved (g) / volume of the 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 paste in the fluid containing supercritical carbon dioxide is not particularly limited, but is preferably 1×10 -5 g / ml or more, 1×10 -4 g / ml or more, or 1×10 -3 The solubility of the paste in the fluid containing supercritical carbon dioxide is not particularly limited, but may be 1 g / ml or less, 1×10 -1 g / ml or less, or 1×10 -2 The above numerical ranges may be combined in any manner.

[0050] In this embodiment, the desizing step can include moving the sizing-coated textile product by power. By moving the sizing-coated textile product by power, a kneading effect can be imparted to the entire sizing-coated textile product (fabric), improving the desizing properties. The power source is not particularly limited, but wind power, electricity, etc. can be used, and among these, wind power is preferred.

[0051] The method of the present embodiment can be used as a desizing process, which is one of the fiber processing steps, and can also be used in combination with other fiber processing steps such as spinning, weaving, sizing, refining / bleaching, dyeing, and finishing. The method of producing a fiber product from a sizing fiber product of the present embodiment can also be combined with the above-mentioned method of producing a sizing fiber product to form a single method or production method.

[0052] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the contents described in the examples. EXAMPLES

[0053] 1. Measurement of physical properties or observation of surface condition of sizing agent or sizing agent-attached textile products (1) Preparation of an aqueous solution containing a sizing agent The adhesives used are shown below. Cellulose ether (1): Metrose (registered trademark) SM-1500 (methylcellulose, weight average molecular weight: 90,000, degree of substitution of methoxy group: 1.8, manufactured by Shin-Etsu Chemical Co., Ltd.) Cellulose ether (2): Metolose (registered trademark) 60SH-06 (hydroxypropyl methylcellulose, weight average molecular weight: 80,000, degree of substitution of methoxy group: 1.9, molar substitution number of hydroxypropoxy group: 0.25, manufactured by Shin-Etsu Chemical Co., Ltd.) Starch paste: A paste containing cornstarch (weight average molecular weight: 500,000-1,000,000) as the main starch, and additives (content of each ingredient in the paste: 2% wax by weight, 1% glycerin by weight, small amount of PVA added).

[0054] [Example 1] Boiling water was added to the cellulose ether (1) to give a dilution ratio of 40 times based on the weight of the cellulose ether, and the resulting diluted solution was stirred for a certain period of time. Room temperature water was added to the diluted solution after stirring to give a dilution ratio of 60 times based on the weight of the cellulose ether, and the resulting diluted solution was stirred for a certain period of time to prepare an aqueous solution with a solid concentration of cellulose ether (1) of 1.0 wt%. [Example 2] An aqueous solution of cellulose ether (2) having a solids concentration of 1.0% by weight was prepared in the same manner as in Example 1, except that the cellulose ether (2) was used instead of the cellulose ether (1). [Example 3] Boiling water was added to the cellulose ether (2) to give a dilution ratio of 8 times based on the weight of the cellulose ether, and the resulting diluted solution was stirred for a certain period of time. Room temperature water was added to the diluted solution after stirring to give a dilution ratio of 12 times based on the weight of the cellulose ether, and the resulting diluted solution was stirred for a certain period of time to prepare an aqueous solution with a solid concentration of cellulose ether (2) of 5.0% by weight. [Comparative Example 1] Water was added to the above starch paste, and the mixture was heated to 90° C. or higher to dissolve and gelatinize the starch paste, thereby preparing an aqueous solution with a starch paste solids concentration of 2.0% by weight.

[0055] (2) Equipment and reagents The sizing machines used were a Minisizer DCI001P (manufactured by Kaji Seisakusho Co., Ltd.) and an HGA-357 sizing machine (manufactured in China, glue tank capacity approximately 47 L).

[0056] (3) Operation procedure [Example 1] Into the above-mentioned sizing machine: Minisizer DCI001P, 2500 ml of the aqueous solution of the cellulose ether of Example 1 obtained in (1) above was placed. In addition, cotton yarn (1) manufactured by Izawa Towel Co., Ltd. (raw silk (unbleached yarn, spun yarn, etc.), 100% cotton, 20 count, single yarn, twist coefficient 4.5, average fiber length about 25 mm) fed from a cheese bobbin was put into the above-mentioned 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. Thereafter, the cotton yarn with the size solution (aqueous solution) attached thereto was passed through a squeezing roll (first pass roll) under a pressure load of 0.04 MPa and an immersion roll (second pass roll) under a pressure load of 0.06 MPa, and further passed through a hot air drying section with a temperature of 110°C and a drying chamber length of about 3.8 m, and a cylinder roll drying section with a temperature of 110°C and a diameter of 100 mm x 7 at a speed of 10 m / min, thereby performing sizing treatment. For the resulting dried (sized) cotton thread (1), the weight of the cotton thread (1) per unit length was measured.

[0057] [Comparative Example 1] 35 L of the aqueous solution of starch paste of Comparative Example 1 obtained in (1) above was placed in the above-mentioned sizing machine: HGA-357 type sizing machine. In addition, cotton yarn (1) manufactured by Izawa Towel Co., Ltd. (raw silk (unbleached yarn, spun yarn, etc.), 100% cotton, 20 count, single yarn, twist coefficient 4.5, average fiber length about 25 mm) fed from a cheese bobbin was put into the aqueous solution of starch paste in the sizing machine. At this time, the weight of the cotton yarn (1) per unit length fed from the cheese bobbin was measured. Thereafter, the cotton yarn with the paste solution (aqueous solution) attached was passed through a drying chamber of about 20 m and dried at 300°C, and then excess paste was removed by a cylinder roll at about 120°C, and the resulting sized cotton yarn (1) was wound on a weaving beam. The passing speed of the cotton yarn in the drying chamber and the cylinder roll was 30 m / min. The weight of the cotton yarn (1) per unit length obtained after drying (after sizing) was measured for the cotton yarn (1) obtained after sizing.

[0058] [Examples 2 and 3] Into the above-mentioned sizing machine: Minisizer DCI001P, 2500 ml of the aqueous solution of each of the cellulose ethers of Examples 2 and 3 obtained in (1) above was placed. In addition, cotton yarn (2) (raw silk, 20 count, single yarn, combed using long cotton, containing less short fibers and less fluff than the cotton yarn (1)) manufactured by Izawa Towel Co., Ltd., fed from a cheese bobbin was introduced into each of the aqueous solutions of cellulose ether in the sizing machine. At this time, the weight of the cotton yarn (2) fed from the cheese bobbin per unit length was measured. Thereafter, sizing treatment was carried out in the same manner as the sizing treatment of the cotton yarn in Example 1 above. The weight of the cotton yarn (2) per unit length obtained after drying (after sizing) was measured.

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

[0060]

number

[0061] (4-3) Abrasion resistance (number of frictions) For each of the sized yarns in Examples 1 to 3 and Comparative Example 1, abrasion resistance was measured using a consolidation tester (1065, manufactured by Maeda Manufacturing Co., Ltd.) based on JIS L 1095:2010 (9.10 Abrasion resistance method B). Specifically, an abrasion test was performed based on the following test conditions, and the number of frictions until two of the 20 samples were broken was measured. <Test conditions> ·Friction speed: 120 times / min ·Friction angle: 110 degrees ·Round distance: 2.5cm Test length: 20cm Friction element: 0.6mm diameter hard steel wire

[0062] (4-4) Single yarn tensile strength and elongation For each of the sized yarns of Examples 1 to 3 and Comparative Example 1, a tensile tester (Autograph AG-Xplus, manufactured by Shimadzu Corporation) was used to measure the single yarn tensile strength and elongation based on JIS L 1095:2010 (9.5 Single yarn tensile strength and elongation) under the conditions of a gripping distance of 20 cm and a pulling speed of 20 cm / min.

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

[0064] The evaluation results of Example 1 and Comparative Example 1 in the above items (4-1) to (4-4) are shown in Table 1, and the evaluation results of Examples 2 and 3 in the above items (4-1) to (4-4) are shown in Table 2. The results of the SEM observations of Example 1 and Comparative Example 1 in (4-5) above are shown in Figures 2 to 4. Figure 2 is an SEM image (magnification: 150x) of cotton yarn with no sizing agent attached, Figure 3 is an SEM image (magnification: 200x) of cotton yarn with starch sizing 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] From the results in Table 1, the aqueous solution containing cellulose ether (1) in Example 1 had a higher viscosity and a suitable viscosity than the aqueous solution containing starch paste in Comparative Example 1. A suitable viscosity provides good permeability, reduces fuzzing as a whole, and exhibits convergence. Therefore, from the above results, it was found that the aqueous solution containing cellulose ether (1) is optimal as a paste from the viewpoint of efficiency during weaving.

[0068] Furthermore, the results in Table 1 show that the cotton yarn with cellulose ether (1) of Example 1 had approximately 120% more friction cycles and was superior in abrasion resistance than the cotton yarn with starch paste of Comparative Example 1. The single-yarn tensile strength of the cotton yarn of Example 1 was approximately 3% lower than that of the cotton yarn of Comparative Example 1, but could be considered equivalent, and was at a practically acceptable level for a cotton yarn with a paste. Furthermore, the cotton yarn of Example 1 had approximately 20% higher elongation than the cotton yarn of Comparative Example 1, showing superior elongation. As shown in Table 1, the adhesion rate of the starch paste (cellulose ether (1)) to the cotton yarn of Example 1 was about half that of the starch paste (starch paste) to the cotton yarn of Comparative Example 1. Despite this low adhesion rate of the starch paste, as described above, the cotton yarn of Example 1 was found to exhibit physical properties equal to or superior to those of the cotton yarn of Comparative Example 1. From these results, it was found that by using the cellulose ether of the present invention as a starch paste, it is possible to impart excellent physical properties to the cotton yarn while reducing the amount of starch paste used and suppressing costs and environmental load.

[0069] As described above, the starch paste used in Comparative Example 1 requires the addition of ingredients such as wax, propylene glycol, polyvinyl alcohol (PVA) other than the starch main ingredient corn starch to improve the convergence, smoothness, flexibility, etc. of the fibers, which leads to the complexity of the formulation and increased costs. On the other hand, the results in Table 1 show that the cellulose ether (1) in Example 1 can improve the convergence, smoothness, flexibility, etc. of the fibers even when the sizing agent is made of cellulose ether (1) without adding any ingredients other than cellulose ether (1), and has performance not found in conventional starch pastes.

[0070] In addition, the SEM photograph in Figure 4 shows that when cellulose ether (1) was used as the sizing agent, fuzzing was suppressed and the entire paper was fixed by the sizing agent. On the other hand, the SEM photograph in Figure 3 shows that when starch paste was used as the sizing agent, fuzzing was not completely suppressed and the convergence was inferior to that of cellulose ether (1). From the results of Table 1 and FIGS. 2 to 4 above, it was found that the cellulose ether of the present invention has a low viscosity and good impregnation property, and has excellent convergence property even when the adhesion rate of the sizing agent is low.

[0071] In addition, the results in Table 2 show that the aqueous solution containing the cellulose ether (2) can be used as a sizing agent. The results in Tables 1 and 2 show that the cellulose ether (A) of the present invention is useful as a sizing agent regardless of its type.

[0072] 2. Evaluation of weaving properties of textile products with sizing agent In addition, as shown in 1 above, the cotton yarn of Example 1 exhibits physical properties equivalent to or superior to those of the cotton yarn of Comparative Example 1, and therefore it can be estimated that the speed at which the cotton yarn of Example 1 and the cotton yarn of Comparative Example 1 can be woven on an air jet loom is equivalent (approximately 350 to 400 rpm). As a result, it can be estimated that the production volume of woven towels per day (8 hours) is also equivalent (approximately 30 to 50 kg) between the cotton yarn of Example 1 and the cotton yarn of Comparative Example 1. As described in the analysis results of the SEM photographs above, the cotton yarn of Example 1, in which fluff is almost completely suppressed, is less likely to pill during weaving and there is less risk of thread breakage, compared to the cotton yarn of Comparative Example 1, in which fluff is generated. From the above, it was found that by using the cellulose ether of the present invention as a sizing agent, it is possible to reduce the amount of sizing agent used, thereby suppressing costs and environmental load, while maintaining the production efficiency of textile fabrics.

[0073] 3. Environmental assessment of gluing process When using starch paste with an adhesion rate of 3% by weight as in Comparative Example 1 and performing sizing processing on 450 kg of cotton yarn (20 count, single yarn), it is estimated that the sizing machine needs to be operated under the following conditions: water usage: 675 L, processing time: 1 hour, and processing temperature: 95 to 120°C. In this case, if the output of the motor that runs the glue machine is 8kW, the electricity cost is 23 yen / kWh, and the CO2 emission coefficient is 0.47kg / kWh, the power consumption can be calculated as 8 (kW) x 1 (hour) = 8 (kWh).As a result, the electricity cost required to operate the glue machine is 23 (yen / kWh) x 8 (kWh) = 184 (yen), and the CO2 emissions during operation of the glue machine are 0.47 (kg / kWh) x 8 (kWh) = 4 (kg). It is also estimated that 608 kg of steam will need to be used to raise the temperature to 95-120°C. The amount of heat required to pressurize 20°C water to turn it into steam is estimated to be 2607 kJ / kg, so the amount of heat required to raise the temperature can be calculated as 608 (kg) x 2607 (kg / kg) x 1 / 1000 = 1584 (MJ). When city gas is used to raise the temperature of the steam, the lower heating value of city gas is 40.3 MJ / m 3 , CO2 emission coefficient: 2.23kg / m 3 , Fuel cost: 100 yen / m 3 If the boiler efficiency is 0.9, the amount of city gas used is 1584 (MJ) ÷ 0.9 ÷ 40.3 (MJ / m 3 )=44(m 3 As a result, the cost of city gas required to raise the temperature is 44(m 3 )×100(yen / m 3 ) = 4400 (yen), and the amount of CO2 emitted during heating is 44 (m 3 )×2.23(kg / m 3 ) = 97(kg).

[0074] Starch paste such as that in Comparative Example 1 is insoluble in water at room temperature (20°C) and must be heated to around 90°C to dissolve and gelatinize, making the above-mentioned heating process using steam necessary. On the other hand, the cellulose ether of the present invention has the property that it is difficult to dissolve in high-temperature liquids such as hot water, but is easily soluble in low-temperature liquids such as cold water and water at room temperature. Therefore, when methylcellulose is used as a sizing agent as in Example 1, sizing at room temperature (20°C) is preferable, and the above-mentioned work of raising the temperature using steam is unnecessary. Therefore, in the case of Example 1, the above-mentioned city gas fee of 4,400 yen and CO2 emission of 97 kg associated with the work of raising the temperature are unnecessary, and energy consumption and CO2 emission can be reduced, thereby reducing the environmental load.

[0075] 4. Measurement of BOD and COD of aqueous solution containing sizing agent An aqueous solution having a solids concentration of 1.0% by weight of cellulose ether (1) was prepared using the cellulose ether (1) described in 1.(1) above, according to the same procedure as in 1.(1) above. Also, an aqueous solution having a solids concentration of 1.0% by weight of starch paste was prepared using the starch paste described in 1.(1) above, by adding water to the starch paste and then heating to 90°C or higher to dissolve and gelatinize the starch paste. For each aqueous solution of methyl cellulose or starch paste, the BOD (biochemical oxygen content) and COD (chemical oxygen content) were measured based on (21. Biochemical oxygen consumption (BOD)) and (17. Oxygen consumption (COD) by potassium permanganate at 100°C) of JIS K 0102:2016. The results are shown in Table 3. BOD is a value that indicates how much oxygen is required for microbial decomposition. COD is a value that indicates how much oxygen is required when an oxidizing agent (potassium permanganate) is added to cause oxidation. 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 paste can suppress water pollution. As shown in the above Example 1 and Comparative Example 1, by using cellulose ether (1) as a sizing agent, it is possible to impart excellent physical properties to cotton yarn even if the amount used is reduced compared to conventional starch paste. In the tests in Table 3 above, the solids concentrations of cellulose ether (1) and starch paste were the same, but in actual sizing, the amount of cellulose ether (1) used can be reduced, allowing sizing to be performed while further suppressing water pollution.

[0078] 5. Desizing using supercritical carbon dioxide (1) Fabric with starch applied and cotton yarn with starch applied (1-1) Fabric with cellulose ether (2) Boiling water was added to the cellulose ether (2) to give a dilution ratio of about 14 times based on the weight of the cellulose ether, and the resulting diluted solution was stirred for a certain period of time. Room temperature water was added to the diluted solution after stirring to give a dilution ratio of about 34 based on the weight of the cellulose ether, and the resulting diluted solution was stirred for a certain period of time to prepare an aqueous solution with a solid concentration of cellulose ether (2) of 3.0% by weight. A 100% cotton fabric woven with raw silk manufactured by Izawa Towel Co., Ltd. was immersed in an aqueous solution containing cellulose ether (2) having a solids concentration of 3.0% by weight obtained as described above. The immersed fabric was passed through the squeezing roll (first pass roll) and immersion roll (second pass roll) of the sizing machine: Minisizer DCI001P shown in 1.(2) above under a pressure load of 0.2 MPa to remove excess sizing agent, and dried in a dryer at 100 to 110°C for 30 minutes to prepare a fabric with cellulose ether (2) attached (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): Metolose (registered trademark) 60SH-50 (hydroxypropyl methylcellulose, weight average molecular weight: 80000, degree of substitution of methoxy group: 1.9, molar substitution of hydroxypropoxy group: 0.25, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared, and boiling water was added to the cellulose ether (3) so that the dilution ratio was about 20 times based on the weight of the cellulose ether, and the resulting diluted solution was stirred for a certain period of time. Room temperature water was added to the diluted solution after stirring so that the dilution ratio was about 30 times based on the weight of the cellulose ether, and the resulting diluted solution was stirred for a certain period of time to prepare an aqueous solution with a solid concentration of cellulose ether (3) of 2.0% by weight. A 100% cotton fabric woven with raw silk manufactured by Izawa Towel Co., Ltd. was immersed in an aqueous solution containing cellulose ether (3) having a solids concentration of 2.0% by weight obtained as described above. The immersed fabric was passed through the squeezing roll (first pass roll) and immersion roll (second pass roll) of the sizing machine: Minisizer DCI001P shown in 1.(2) above under a pressure load of 0.2 MPa to remove excess sizing agent, and dried in a dryer at 100 to 110°C for 30 minutes to prepare a fabric with cellulose ether (3) attached (sizing agent adhesion rate calculated based on formula (1) in 1.(4-2) above: 1.69%).

[0080] (1-3) Cotton yarn with cellulose ether (3) In addition, 2500 ml of the aqueous solution of cellulose ether (3) obtained in (1-2) above, in which the solid content concentration was 〇% by weight, was placed in the sizing machine: Minisizer DCI001P shown in (2) above in 1. Then, in the same manner as the sizing method described in [Example 1] in (3) above in 1., cotton yarn (1) (raw silk (unbleached yarn, spun yarn, etc.), 100% cotton, 20 count, single yarn, twist coefficient 4.5, average fiber length about 25 mm) manufactured by Izawa Towel Co., Ltd. was treated to prepare cotton yarn with cellulose ether (3) attached (adhesion rate of starch agent calculated based on formula (1) in (4-2) above: 1.6%).

[0081] (2) Equipment and reagents An overview of the entire apparatus used in the treatment with a fluid containing supercritical carbon dioxide is shown in Figure 5. The symbols in Figure 5 indicate: 1: chiller unit, 2: CO2 supply pump, 3: air vent valve, 4: check valve, 5: pressure transmitter, 6: safety valve, 7: dyeing vessel, 8: vessel drain valve, 9: vessel temperature sensor, 10: magnetic induction type stirrer, 11: exhaust flow rate adjustment valve, 12: vessel exhaust valve, 13: control panel, 14: outlet for CO2 supply pump, 15: outlet for dyeing vessel heater, and A: CO2 cylinder. A cooling water circulation system LTC-450α (manufactured by AS ONE CORPORATION) was used as the chiller unit 1, a double plunger pump NP-KX-500 (manufactured by Nippon Seimitsu Kagaku Co., Ltd.) was used as the CO2 supply pump 2, and a high-pressure vessel (manufactured by ITEC Corporation, model: C-04-M-FU, capacity: 400 ml) was used as the dyeing vessel 7. A liquefied carbon dioxide cylinder (Kind Gas Co., Ltd., purity 99.5% or higher) was used as the carbon dioxide supply source.

[0082] (3) Operation procedure (3-1) Fabric with cellulose ether (2) attached A jig (110 cm long x 15 mm outer diameter, hollow cylinder, mesh structure, made of metal) was prepared, and the fabric (approximately 10 cm x approximately 10 cm, approximately 2 g) to which the cellulose ether (2) described in (1-1) above was attached was wrapped around the jig. A cotton string was further wrapped around the wrapped fabric to secure it in place. Figure 6 (a) shows the jig with the fabric wrapped around it. In addition, an outer cylinder (a hollow cylinder with a length of 110 cm, an inner diameter of 36 mm, and an outer diameter of 41 mm) was prepared, and a paper wiper (Kimwipe (registered trademark), 120 mm x 210 mm) that had been soaked evenly with 1 ml of water as a co-solvent was wrapped around the outside of the outer cylinder. A cotton string was further wrapped around the wrapped paper wiper to secure it in place. Figure 6 (b) shows the outer cylinder with the paper wiper wrapped around it. The jig wrapped with the fabric was placed and fixed inside the outer cylinder wrapped with a paper wiper to obtain a measurement sample. The obtained measurement sample was placed in the dyeing vessel 7. Next, 200 ml of carbon dioxide was sent to the dyeing vessel 7 at a liquid sending rate of 20 to 300 ml / min using the CO2 supply pump 2 to pressurize the dyeing vessel 7. The conditions for treating the measurement sample with supercritical carbon dioxide fluid were 40°C, 10 MPa, time 120 minutes, batch type, and stirring was performed using a propeller, with one set of 60 seconds of forward rotation and 60 seconds of reverse rotation, and this set was repeated at 900 rpm for 120 minutes. The water soaked in the paper wiper was mixed with supercritical carbon dioxide, and the volume ratio of supercritical carbon dioxide:water was 200:1. After treatment with supercritical carbon dioxide fluid, the valve of the dyeing vessel 7 was opened to release pressure to atmospheric pressure. After the pressure in the dyeing vessel 7 was released, the fabric was taken out of 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 tool similar to that used in the treatment of (3-1) above was prepared, and the fabric (approximately 10 cm x approximately 10 cm, approximately 8 g) to which the cellulose ether (3) shown in (1-2) above had been attached was wrapped around the tool. A cotton string was further wrapped around the wrapped fabric to secure it in place. The jig with the fabric wrapped around it was in the same state as in Figure 6 (a). In addition, an outer cylinder similar to that used in the above treatment (3-1) was prepared, and a paper wiper (Kimwipe (registered trademark), 120 mm x 210 mm) that had been soaked evenly throughout with 5 ml of the co-solvent EGME (ethylene glycol monobutyl ether) was wrapped around the outside of the outer cylinder. A cotton string was further wrapped around the wrapped paper wiper to secure it in place. The outer cylinder with the paper wiper wrapped around it was in the same state as in Figure 6 (b). The jig wrapped around the fabric was placed and fixed inside an outer cylinder wrapped around a paper wiper to obtain a measurement sample. The obtained measurement sample was placed in a dyeing vessel 7, and the measurement sample was treated with supercritical carbon dioxide fluid in the same manner as in the above (3-1), except that the conditions for treating the measurement sample with supercritical carbon dioxide fluid were 120°C, 25MPa, 180 minutes, and batch-type instead of 40°C, 10MPa, and 120 minutes, and the measurement sample was treated with supercritical carbon dioxide fluid. The EGME soaked in the paper wiper was mixed with supercritical carbon dioxide, and the volume ratio of supercritical carbon dioxide:fabric was 45:1, and the volume ratio of supercritical carbon dioxide:EGME was 80:1. After the treatment with supercritical carbon dioxide fluid, the valve of the dyeing vessel 7 was opened to release the pressure to atmospheric pressure. After releasing the pressure in the dyeing vessel 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 with cellulose ether (3) A jig similar to that used in the treatment of (3-1) above was prepared, and the cotton thread (length: about 400 m, about 10 g) to which the cellulose ether (3) shown in (1-3) above was attached was wound around the jig. A cotton string was further wrapped around the wound cotton thread to secure it in place. Figure 7 shows the jig with the cotton thread wrapped around it. In addition, an outer cylinder similar to that used in the above treatment (3-1) was prepared, and a paper wiper (Kimwipe (registered trademark), 120 mm x 210 mm) that had been soaked evenly throughout with 5 ml of the co-solvent EGME (ethylene glycol monobutyl ether) was wrapped around the outside of the outer cylinder. A cotton string was further wrapped around the wrapped paper wiper to secure it in place. 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 the paper wiper wrapped around it to obtain a measurement sample. The obtained measurement sample was placed in the dyeing vessel 7, and the measurement sample was treated with supercritical carbon dioxide fluid in the same manner as in the treatment in (3-2) above. The EGME soaked in the paper wiper was mixed with supercritical carbon dioxide, and the volume ratio of supercritical carbon dioxide:cotton yarn was 40:1, and the volume ratio of supercritical carbon dioxide:EGME was 80:1. After treatment with supercritical carbon dioxide fluid, the valve of the dyeing vessel 7 was opened to release pressure to atmospheric pressure. After releasing pressure in the dyeing vessel 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) Sizing agent removal rate First, the weight (g) of the fabric or cotton yarn before sizing and desizing and the weight (g) of the fabric or cotton yarn after desizing were used to calculate the adhesion rate of cellulose ether (2) or cellulose ether (3) (sizing agent) on the fabric or cotton yarn after desizing based on the above-mentioned formula (1) described in 1.(4-2) above. Then, using the size adhesion rate (%) of the sizing 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 size adhesion rate (%) of the fabric or cotton yarn after the desizing treatment as described above, the size removal rate (Desizing rate D) was calculated based on the following formula (2).

[0086]

number

[0087] The calculated removal rate of cellulose ether (2) (sizing agent) from the fabric was approximately 12%. This result shows that cellulose ether (2) can be removed by desizing treatment using supercritical carbon dioxide. It is expected that the removal rate of the sizing agent can be further increased by improving the mixing efficiency, increasing the number of batches, etc. In addition, the solubility of cellulose ether (2) (sizing agent) in supercritical carbon dioxide fluid (total of supercritical carbon dioxide and water) (amount of dissolved cellulose ether (2) (sizing agent) (g) / volume of supercritical carbon dioxide fluid (ml)) was calculated to be 3.7 × 10 -5 g / ml.

[0088] The calculated removal rate of cellulose ether (3) (sizing agent) from the fabric was approximately 98%. This result indicates that the cellulose ether (3) can be removed at a very high rate by the desizing treatment using supercritical carbon dioxide with EGME as a co-solvent. In addition, when the same desizing treatment was performed with increasing amounts of EGME added, it was found that the removal rate of cellulose ether (3) (sizing agent) was 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, the solubility of cellulose ether (3) (sizing agent) in supercritical carbon dioxide fluid (total of supercritical carbon dioxide and EGME) (amount of dissolved cellulose ether (3) (sizing agent) (g) / volume of supercritical carbon dioxide fluid (ml)) was calculated to be 3.1 × 10 -3 g / ml.

[0089] The calculated removal rate of cellulose ether (3) (sizing agent) obtained for cotton yarn was about 96%. In addition, the solubility of cellulose ether (3) (sizing agent) in supercritical carbon dioxide fluid (total of supercritical carbon dioxide and EGME) (amount of dissolved cellulose ether (3) (sizing agent) (g) / volume of supercritical carbon dioxide fluid (ml)) was calculated to be 3.5×10 -3 g / ml. Comparing the results for these cotton yarns with those for cellulose ether (3) (sizing agent) on the above-mentioned fabric, it was found that the removal rate and solubility of cellulose ether (3) (sizing agent) did not change regardless of whether fabric or cotton yarn was used as the target for desizing, and that cellulose ether (3) could be removed extremely efficiently.

[0090] (4-2) Observation with a scanning electron microscope Using a tabletop microscope (Miniscope (registered trademark) TM4000Plus, manufactured by Hitachi High-Technologies Corporation) at an accelerating voltage of 15 kV, the surfaces of the fabric to which the cellulose ether (3) described above in (3-2) was adhered, the fabric with the sizing agent adhered thereto before the desizing treatment, and the fabric after the desizing treatment, were observed. The results of SEM observation are shown in Figures 8 and 9. Figure 8 is an SEM image (magnification: 200x) of the fabric with sizing agent attached before desizing treatment, and Figure 9 is an SEM image (magnification: 200x) of the fabric after desizing treatment. Comparing Figures 8 and 9, it can be seen that before the desizing process (Figure 8), the threads were converged due to the sizing agent, but after the desizing process (Figure 9), the threads that make up the fabric have spread out and the convergence has weakened.

[0091] (4-3) Water wettability (water absorbency) Regarding the fabric to which the above (3-2) cellulose ether (3) was attached, the water wettability (water absorbency) of the fabric with the sizing agent attached before the desizing treatment and the fabric after the desizing treatment were evaluated. The water wettability of the fabric was measured according to the drop method of "JIS L 1907 Test method for water absorbency of textile products." Photographs of the fabrics after the evaluation of water wettability are shown in Figure 10. The fabric on the left side of Figure 10 is the fabric with the sizing agent attached before the desizing treatment, and the fabric on the right side of Figure 10 is the fabric after the desizing treatment. As can be seen from Figure 10, in the fabric with the starch attached before the desizing process, water droplets remained on the surface of the fabric, and almost no water absorbency was observed. On the other hand, in the fabric after the desizing process, water was absorbed from the surface of the fabric, and no water droplets remained on the surface. These results show that the desizing process using supercritical carbon dioxide sufficiently removes the cellulose ether starch, allowing the fabric to exhibit its water absorbency.

[0092] From the above, it was found that the fiber product with sizing agent of the present invention has excellent fiber bundling properties. Furthermore, the following points were confirmed from the above results. The sizing textile product of the present embodiment can improve the convergence of the fibers without excessively increasing the amount of adhesive of the sizing textile product, or the sizing textile product of the present embodiment can exhibit high tensile strength, or the sizing textile product of the present embodiment has high durability against friction and is less likely to experience a decrease in tensile strength even after a friction test. The starch paste of the present embodiment can reduce the BOD and / or COD values ​​when dissolved in water compared to conventional starch pastes, thereby preventing water pollution. The method for producing textile products from textile products with sizing agent of the present embodiment can efficiently remove the sizing agent, and can provide textile products with excellent water wettability. [Explanation of symbols]

[0093] 1: Chiller unit 2: CO2 supply pump 3: Air vent valve 4: Check valve 5: Pressure transmitter 6: Safety valve 7: Dyeing vessel 8: Container drain valve 9: Temperature sensor inside the container 10: Magnetic induction stirrer 11: Exhaust flow rate control valve 12: Container exhaust valve 13: Control panel 14: Outlet for CO2 supply pump 15: Outlet for dyeing vessel heater A: CO2 cylinder

Claims

1. A textile product with a sizing agent, The sizing agent comprises at least one cellulose ether (A) selected from the group consisting of methyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose.

2. 2. The sized textile product of claim 1, wherein the textile product comprises cotton yarn or cotton fabric.

3. A sizing agent for producing the sizing fiber product according to claim 1 or 2, comprising at least one cellulose ether (A) selected from the group consisting of methyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose.

4. A method for producing the sizing-applied fiber product according to claim 1 or 2, comprising the steps of: The method includes a step of contacting a textile product with a fluid containing the sizing agent to size the textile product, The method as described above, 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 55°C.

5. A method for producing a textile product from the sizing-applied textile product according to claim 1 or 2, comprising the steps of: The method further comprises a step of contacting the sizing agent-coated textile product with a fluid containing supercritical carbon dioxide to desize the sizing agent-coated textile product.

6. 6. The method of claim 5, wherein the desizing step is by a batch process or a continuous process.

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