Manufacturing method of collagen-processed fibers

Abstract

To provide a novel method of manufacturing collagen processed fiber in which processing by collagen can be efficiently performed to a fiber.SOLUTION: A method of manufacturing collagen processed fiber has: a process S11 of processing fiber by dry process; and a process S21 of bringing aqueous solution containing collagen in contact with the fiber processed by the dry process, and fixing the collagen contained in the aqueous solution to the fiber. A collagen processed fiber in which the fiber is polyester, and a collagen fixed amount is 57 μg / g-fiber or more. A collagen processed fiber in which the fiber is any one selected from a group consisting of polypropylene, polyethylene, modacrylic fiber and vinylon, and a collagen fixed amount is 74 μg / g-fiber or more. A collagen processed fiber in which the fiber is any one selected from a group consisting of nylon, aramid and polyurethane, and a collagen fixed amount is 38 μg / g-fiber or more.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to processed collagen fibers. The present invention also relates to a method for producing the same.

Background Art

[0002] In the global fiber composition ratio, chemical fibers such as polyester and nylon account for more than 70%, and the demand for chemical fibers is expected to increase in the future. On the other hand, there are concerns about the adverse effects of chemical fibers on the skin. In order to improve comfort, processing with proteins having functions such as moisturizing properties using amphoteric compounds that inhibit extreme pH changes has been carried out.

[0003] For example, a moisturizing knit product knitted with fibers integrated with collagen, which is a natural moisturizing component, is known (Patent Document 1). Patent Document 1 discloses a beauty glove containing collagen, characterized in that it is made of fibers containing collagen in the ground knitting yarn of the glove.

[0004] On the other hand, Non-Patent Document 1 describes the amount of collagen fixed in the nylon glove according to Patent Document 1, with a maximum of 35 μg / g-fiber and a fixing rate of only 0.09%.

[0005] Non-Patent Document 2 obtained a film in which various amounts of collagen and aggregates formed from collagen molecules were fixed on a poly(ethylene terephthalate) (PET) film subjected to direct current (DC) helium plasma treatment in order to obtain biocompatibility for tissue repair after injury.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Non-Patent Documents

[0007] [Non-Patent Document 1] Donowaki, "Quantitative Analysis of Collagen Processed into Fibers," Fukuoka Prefectural Industrial Technology Center Research Report No. 31, pp. 1-3 (2021). [Non-Patent Document 2] AFLORI Magdalena et al. “Collagen immobilization on polyethylene terephthalate surface after helium plasma treatment” Materials Science & Engineering. B. Advanced Functional Solid-State Materials, Vol.178, No.19, Page.1303-1310 (2013) [Overview of the project] [Problems that the invention aims to solve]

[0008] Non-patent document 1 describes the amount of collagen adhering to nylon gloves related to patent document 1, stating that the maximum is 35 μg / g-fiber and the adhesion rate is a mere 0.09%. On the other hand, as described in non-patent document 2, various amounts of collagen and aggregates formed from collagen molecules may have a positive effect on tissue repair after injury. Therefore, if textile products such as gloves with increased collagen adhering can be provided, they can be expected to be developed not just as general-purpose gloves, but also as medical textile products.

[0009] Under these circumstances, the present invention aims to provide a new method for producing collagen-processed fibers that can improve the adhesion of collagen to fibers. [Means for solving the problem]

[0010] The inventors of this invention have conducted extensive research to solve the above problems and have found that the following invention is suitable for the above purpose, leading to the present invention. That is, the present invention relates to the following invention.

[0011] <1> The process of treating fibers by a dry process, A method for producing collagen-processed fibers, comprising the step of contacting the fibers treated by the dry process with an aqueous solution containing collagen to fix the collagen contained in the aqueous solution to the fibers. <2> The dry process is one of the processes selected from the group consisting of plasma treatment, corona treatment, ultraviolet treatment, ozone treatment, electron beam treatment, and flame treatment. <1> The manufacturing method described above. <3> The fiber is one of the fibers selected from the group consisting of polyester, polypropylene, polyethylene, modacrylic, vinylon, nylon, aramid, and polyurethane. <1> or <2> The manufacturing method described above. <4> The crosslinking agent for the fiber and the collagen, which crosslinks the fiber and the collagen. <1> ~ <3> A manufacturing method described in any of the following. <5> The aforementioned processing step further involves processing the collagen by a dry process. <1> ~ <4> A manufacturing method described in any of the following. <6> A collagen-processed fiber in which collagen is fixed to a fiber, wherein the fiber is polyester and the amount of fixed collagen is 57 μg / g-fiber or more. <7> A collagen-processed fiber in which collagen is fixed to a fiber, wherein the fiber is selected from the group consisting of polypropylene, polyethylene, modacryl, and vinylon, and the amount of fixed collagen is 74 μg / g-fiber or more. <8> A collagen-processed fiber in which collagen is fixed to a fiber, wherein the fiber is selected from the group consisting of nylon, aramid, and polyurethane, and the amount of fixed collagen is 38 μg / g-fiber or more. <9> The fiber comprises a crosslinking agent for the collagen. <6> ~ <8> Collagen-processed fiber as described in any of the following. <10> The process of treating fibers by a dry process, A method for producing collagen-processed fibers, comprising the step of contacting the fibers treated by the dry process with an aqueous solution containing collagen to fix the collagen contained in the aqueous solution to the fibers, The dry process is one of the processes selected from the group consisting of plasma treatment, ultraviolet treatment, and flame treatment. The aforementioned fiber is one of the fibers selected from the group consisting of polyester, polypropylene, polyethylene, modacrylic, vinylon, nylon, aramid, and polyurethane. A method for producing a crosslinking agent between the fiber and the collagen, wherein the crosslinking agent is a blocked isocyanate crosslinking agent. <11> A process of processing fibers and collagen using a dry process, A method for producing collagen-processed fibers, comprising the step of contacting the fibers processed by the dry process with an aqueous solution containing the collagen processed by the dry process, thereby fixing the collagen contained in the aqueous solution to the fibers, The dry process is one of the processes selected from the group consisting of plasma treatment, ultraviolet treatment, and flame treatment. A method for producing the aforementioned fibers, wherein the fibers are selected from the group consisting of polyester, polypropylene, polyethylene, modacrylic, vinylon, nylon, aramid, and polyurethane. <12> The crosslinking agent for the fiber and the collagen, which crosslinks the fiber and the collagen. <11> The manufacturing method described above. [Advantages of the Invention]

[0012] According to the production method of the present invention, the adhesion of collagen to the collagen-treated fiber can be improved. [Brief Description of the Drawings]

[0013] [Figure 1] It is a flowchart showing an example of the production method of the present invention. [Embodiments for Carrying Out the Invention]

[0014] Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to the following contents unless the gist thereof is changed. In this specification, when the expression "~" is used, it is used as an expression including the numerical values before and after it.

[0015] [Production Method of the Present Invention] The production method of the present invention is a method for producing collagen-treated fibers, which includes a step of treating fibers by a dry process and a step of bringing an aqueous solution containing collagen into contact with the fibers to fix the collagen contained in the aqueous solution to the fibers.

[0016] [Collagen-Treated Fibers of the Present Invention] The collagen-treated fibers of the present invention are collagen-treated fibers in which collagen is fixed to fibers. They are made using a predetermined type of fiber, and have a collagen fixation amount greater than a predetermined amount, which is more than conventional, according to the type of each fiber.

[0017] The manufacturing method of the present invention is an efficient method for producing collagen-processed fibers. Furthermore, the collagen-processed fibers of the present invention have a high collagen fixation amount and excellent moisturizing properties. In addition, the collagen-processed fiber product of the present invention can also be obtained by the manufacturing method of the present invention, and the corresponding components in this application can be used interchangeably.

[0018] Collagen-processed fibers are expected to be used in applications that come into direct contact with the skin. However, conventional knit fiber products such as nylon have a low amount of collagen fixation, so if the amount of collagen fixation can be improved, it is expected that the technology can be expanded to medical fiber products and other applications. The inventors hypothesized that the fiber-protein interaction in the fiber processing bath can be improved by subjecting the fibers to an appropriate dry process treatment beforehand. Furthermore, they believed that efficient processing could be achieved by performing a crosslinking reaction after the interaction has been improved, and that this could result in a low-environmental-impact fiber processing technology by reducing the amount of collagen and crosslinking agent required. In addition, they found that this efficient crosslinking reaction can also improve the washing durability of collagen-processed fibers.

[0019] [Manufacturing flow of the present invention] Figure 1 is a flowchart showing an example of the manufacturing method of the present invention. The manufacturing method of the present invention includes step S11, in which the fibers are treated by a dry process. Subsequently, step S21 is in which the interaction between the fibers and collagen is improved in a solution, and the treated fibers and collagen are cross-linked to fix the collagen.

[0020] [Dry process] The manufacturing method of the present invention includes a step of treating the fibers by a dry process. By performing this dry process treatment, the amount of collagen fixed to the fibers can be increased. In addition, the collagen can also be treated by a dry process in this step. The manufacturing method of the present invention allows for selective treatment of areas where an increase in collagen fixation is desired, and this can be a part of the fiber or the entire fiber. Furthermore, since the dry process can be performed on fibers in the shape of the product, there is no loss of collagen-processed yarn such as threads used when manufacturing primary fiber products, and no loss of collagen-processed fabric such as scraps when manufacturing secondary fiber products.

[0021] [fiber] The term "fibers" can refer to primary textile products such as yarn, woven fabrics, knitted fabrics, and nonwoven fabrics, as well as secondary textile products such as apparel and general merchandise. Any type of fiber can be used, including synthetic fibers and natural fibers. It is particularly preferable to use synthetic fibers. Synthetic fibers can be selected from the group consisting of, for example, polyester, polypropylene, polyethylene, modacrylic, vinylon, nylon, aramid, polyurethane, acetate, and rayon. Polyester can include, for example, polyethylene terephthalate or polytrimethylene terephthalate. Cotton, linen, silk, and wool may also be used. Furthermore, blends of synthetic fibers and / or natural fibers, or other components, may also be used.

[0022] [Types of dry processes] The dry process can be any of the following: plasma treatment, corona treatment, ultraviolet treatment, ozone treatment, electron beam treatment, and flame treatment. Among these, plasma treatment, corona treatment, ultraviolet treatment, ozone treatment, and flame treatment are preferred.

[0023] Dry processes can alter (modify) the properties of fibers in a dry state, offering advantages such as eliminating the need for water or chemical addition, disposal of those substances, and drying processes. All of the dry processes described above are expected to improve wettability. For example, processing in air can shift the surface potential of the fibers to a negative value. Furthermore, the type of gas used can alter the functional groups substituted into the fibers, potentially shifting the potential not only to the negative side but also to the positive side.

[0024] Plasma treatment is a process that treats fibers by irradiating them with plasma. It can be performed using low-vacuum plasma treatment with gases such as standard air (Air), nitrogen (N2), or hydrogen (H2) / N2 mixed gas. Furthermore, it can be performed in a vacuum of approximately 10-200 Pa or 20-100 Pa.

[0025] The plasma irradiation time for plasma processing can be 10 seconds or more. The plasma processing time may also be 30 seconds or more, 1 minute or more, or 5 minutes or more. There is no specific upper limit for the plasma irradiation time, but since the effect may saturate if it is done for a long time, and the manufacturing time may be prolonged, an upper limit such as 60 minutes or less, 30 minutes or less, 20 minutes or less, or 15 minutes or less may be set.

[0026] Ultraviolet (UV) treatment is a method of treating fibers by irradiating them with ultraviolet light. It is preferable to use UV light that can generate ozone, and preferably UV light including deep ultraviolet and UV-C (wavelengths of 100-280 nm). For example, low-pressure mercury lamps with wavelengths of 185 nm and 254 nm, or excimer lamps with a wavelength of 172 nm can be used.

[0027] When performing UV treatment, the treatment time may be 30 seconds or more, 1 minute or more, or 5 minutes or more. There is no specific upper limit for UV irradiation time, but since prolonged irradiation may cause the effect to saturate or the temperature to become too high, damaging the fibers, an upper limit such as 60 minutes or less, 30 minutes or less, 20 minutes or less, or 15 minutes or less may be set, or multiple sessions may be performed with intervals in between. The irradiation intensity should be several mW / cm². 2 From tens of mW / cm 2 This can be used as a guideline; the higher the value, the greater the amount of modification and the faster the modification time, and it is preferable to adjust it along with the irradiation distance to the object being treated. When ultraviolet treatment is performed in air, it is thought that the oxygen in the air is converted into ozone, and the modification occurs when the ozone combines with the object being treated.

[0028] Based on the modification mechanism of UV treatment described above, ozone treatment operates on a similar mechanism, and a similar modification effect can be expected by using an ozone generator. Furthermore, because the temperature does not rise, it is expected to cause less damage to the fibers than UV treatment.

[0029] Flame treatment is a process that modifies the surface of a material by burning a flammable gas containing silicone or silica to form a silicon oxide film. This process is carried out by reciprocating motion so that the gas strikes the material parallel to it to ensure uniform surface treatment. The number of reciprocations may be two or more, four or more, or sixteen or more. There is no specific upper limit on the number of treatment cycles, but since increasing the number of cycles may lead to saturation of the effect or damage to the fibers from the flame, an upper limit such as 100 or 50 reciprocations may be set. The irradiation intensity can be adjusted by the gas output, but it must be adjusted in conjunction with the distance from the material to be treated.

[0030] [Collagen fixation process] The manufacturing method of the present invention includes a step of contacting a fiber with an aqueous solution containing collagen to fix the collagen contained in the aqueous solution to the fiber. By performing this collagen fixing step, the collagen is fixed to the fiber. This fixing includes fixing through interactions between the fiber and collagen, as well as fixing through crosslinking by a crosslinking agent on either the fiber or the collagen, or both.

[0031] [Collagen ingredients] The collagen concentration in the aqueous solution is preferably 0.01%owf to 30%owf (on the weight of fiber). If the collagen concentration is too low, the amount of collagen that adheres may not be sufficient. The lower limit of the collagen concentration is preferably 0.05%owf or higher, and more preferably 0.08%owf or higher. If the collagen concentration is too high, there is a risk of loss of collagen that remains unadhered. The upper limit of the collagen concentration can be 20%owf or lower, 10%owf or lower, 5%owf or lower, etc.

[0032] The means of contact between the aqueous solution and the fibers, the contact temperature, and the contact time can be appropriately determined by using techniques employed in collagen-processed fibers, depending on the combination of these factors, the amount of collagen fixed, the condition of the fibers, and the processing equipment. For example, contact may be made by immersing the fibers in an aqueous solution contained in a liquid tank or by spraying the aqueous solution onto the fibers.

[0033] Furthermore, the contact temperature during contact can be set considering factors such as the ease with which collagen dissolves, the low risk of fiber damage, and the ease of handling due to minimal changes in aqueous solution concentration. This temperature is preferably controlled by adjusting the temperature of the aqueous solution. For example, contact can be made with an aqueous solution at room temperature to around 80°C or 40 to 70°C. The contact time can also be appropriately set within the range in which collagen adheres, depending on the various conditions during contact as described above. For example, it can be set to around 1 minute to 2 hours or 10 minutes to 1 hour.

[0034] [Crosslinking agent] The aqueous solution may contain a crosslinking agent. The crosslinking agent can be a commercially available agent used for bonding fibers and collagen, such as glutaraldehyde, cyanuryl chloride, epoxy crosslinking agents, or blocked isocyanate crosslinking agents. For example, epoxy crosslinking agents include ethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and Denacol EX-321 from Nagase ChemteX Corporation. Blocked isocyanate crosslinking agents such as SU-315V from Meisei Chemical Industry Co., Ltd., BAYPRET® USV from Tanatex Chemical Japan Co., Ltd., and MERSTARK372N from Kitahiro Chemical Co., Ltd. can be used.

[0035] The crosslinking agent can be used by any means that contributes to the crosslinking of collagen and fibers. For example, it can be included in an aqueous solution used in the fixing process. Alternatively, the aqueous solution may already contain collagen and the crosslinking agent. Or, the fibers may be brought into contact with the collagen-containing aqueous solution, and then the crosslinking agent may be added to fix them while crosslinking. Alternatively, the fibers that have been pre-treated with the collagen-containing aqueous solution may be dried, and then the pre-treated fibers may be brought into contact with the crosslinking agent aqueous solution to fix them while crosslinking.

[0036] The concentration of the crosslinking agent, processing time, and processing temperature can be appropriately set according to the type of crosslinking agent, fiber, collagen, and the amount of fixation. Each crosslinking agent has standard usage conditions, such as whether dilution is possible and the dilution concentration, based on the active ingredient concentration, and processing can be carried out in accordance with these conditions. For example, depending on the usage of the crosslinking agent, the processing temperature and processing time can be appropriately set according to the conditions for fixation using an aqueous solution containing collagen.

[0037] Thus, the manufacturing method of the present invention is a method for producing collagen-processed fibers. By processing the fibers using a dry process, collagen can be efficiently fixed to the fibers. This allows for at least one of the advantages of efficient collagen fixation, such as improved fixation amount and fixation rate, improved washability, reduced raw material loss, shortened processing time, and relaxed processing conditions. This can be done with fibers of any shape. Thus, the manufacturing method of the present invention is an environmentally friendly processing technology that improves and controls fiber-protein interactions using a dry process.

[0038] [Collagen-processed fiber] The collagen-processed fiber of the present invention is a collagen-processed fiber in which collagen is fixed to a fiber, and uses a predetermined type of fiber, with a predetermined amount of collagen fixed to each fiber type that is greater than conventional amounts. A higher amount of collagen fixed is expected to result in higher moisturizing properties. The amount of collagen fixed in the collagen-processed fiber of the present invention may have a lower limit set for each fiber.

[0039] In collagen-processed fibers, the amount of collagen fixed can be determined by classifying the fibers into the following types and setting the amount of fixation for each type. (Fiber type A) Polyester (Fiber Type B) Fibers whose chemical formula has the structure of formula (1) in the main chain, etc., such as polypropylene (R is CH3), polyethylene (R is H), acrylic and modacrylic (R is CN), and vinylon (R is OH). The structure of R in formula (1) is also shown for each fiber. Also, n in formula (1) is the number of repeats which is appropriately designed for each fiber. (Fiber type C) Fibers having the bonding structure (amide bond) of formula (2) in their chemical formula: nylon, aramid, and polyurethane.

[0040] [ka]

[0041] [ka]

[0042] (Fiber type A) Polyester The collagen-processed fiber of the present invention is made of polyester, and the amount of collagen fixed can be 57 μg / g-fiber or more. The lower limit of the amount of collagen fixed may be 80 μg / g-fiber or more, 100 μg / g-fiber or more, 200 μg / g-fiber or more, or 300 μg / g-fiber or more. The upper limit of the amount of collagen fixed may be 4000 μg / g-fiber or less, or 3000 μg / g-fiber or less.

[0043] The amount of collagen fixed to polyester (fiber type A) will be explained below, referring to the measurement examples in the examples described later. For example, in the case of polyester, when a crosslinking agent is added, the amount of collagen fixed is 56 μg / g-fiber (Table 3 below), but by performing plasma treatment according to the manufacturing method of the present invention for 5 minutes, the amount of collagen fixed improved to 315 μg / g-fiber (Table 1 below) and 368 μg / g-fiber (Table 3 below). This is thought to be because although the interaction between untreated polyester and collagen was good, crosslinking reactions also occurred between collagen fibers during these crosslinking reactions, causing them to detach during washing. On the other hand, the interaction between the plasma-treated polyester and collagen of the present invention became stronger, which is thought to have improved the amount of collagen fixed. From this, the lower limit of the amount of collagen fixed to the collagen-processed polyester of the present invention can be set to 57 μg / g-fiber or higher with a crosslinking agent. It may also be set to 156 μg / g-fiber or higher, considering the case without a crosslinking agent. The upper limit on the amount of collagen fixed may depend not only on the plasma treatment time but also on the amount of collagen added, the type and amount of crosslinking agent added, and the surface area of ​​the polyester, so it is not necessary to set a specific limit.

[0044] (Fiber type B) Fibers having the structure of formula (1) in their chemical formula The collagen-processed fiber of the present invention is made of any fiber selected from the group consisting of polypropylene, polyethylene, modacryl, and vinylon, and the amount of collagen fixed can be 74 μg / g-fiber or more. The lower limit of the amount of collagen fixed may be 100 μg / g-fiber or more, 150 μg / g-fiber or more, or 200 μg / g-fiber or more. The upper limit of the amount of collagen fixed may be 4000 μg / g-fiber or less, 2000 μg / g-fiber or less, or 1000 μg / g-fiber or less.

[0045] The amount of collagen fixed, etc., will be explained below, referring to the measurement examples in the examples. In the case of polypropylene, which is a representative fiber represented by formula (1), the amount of collagen fixed is 0.1 μg / g-fiber in the untreated state (Table 1 below) and 73 μg / g-fiber when a crosslinking agent is added (Table 3 below). However, by performing plasma treatment for 5 minutes, the fixation improved to 289 μg / g-fiber (Table 1 below) and 274 μg / g-fiber (Table 3 below), respectively. From this, the lower limit of the amount of collagen fixed in the collagen-processed polypropylene of the present invention can be set to 0.2 μg / g-fiber or more without a crosslinking agent, and 74 μg / g-fiber or more with a crosslinking agent. The upper limit of the amount of collagen fixed may depend not only on the plasma treatment time, but also on the amount of collagen added, the type and amount of crosslinking agent added, the surface area of ​​the polypropylene, etc., so it is not necessary to set one.

[0046] (Fiber type C) Fiber having a bonding structure of formula (2) in its chemical formula The collagen-processed fiber of the present invention is made of a fiber selected from the group consisting of nylon, aramid, and polyurethane, and the amount of collagen fixed can be 38 μg / g-fiber or more. The lower limit of the amount of collagen fixed may be 50 μg / g-fiber or more, 80 μg / g-fiber or more, or 100 μg / g-fiber or more. The upper limit of the amount of collagen fixed may be 4000 μg / g-fiber or less, 2000 μg / g-fiber or less, or 1000 μg / g-fiber or less.

[0047] In the case of nylon, a representative fiber having the bond of formula (2), the collagen content is 5 μg / g-fiber in the untreated state (Table 1 below) and 37 μg / g-fiber with the addition of a crosslinking agent (Table 3 below). However, by performing plasma treatment for 5 minutes, these values ​​were reduced to 106 μg / g-fiber (Table 1 below) and 91 μg / g-fiber (Table 3 below), respectively. From this, the lower limit of collagen fixation in the collagen-processed nylon of the present invention can be set to 6 μg / g-fiber or more without a crosslinking agent and 38 μg / g-fiber or more with a crosslinking agent. The upper limit of collagen fixation may depend not only on the plasma treatment time but also on the amount of collagen added, the type and amount of crosslinking agent added, the surface area of ​​the nylon, etc., so it is not necessary to set a specific limit.

[0048] [Method for measuring the collagen concentration of collagen-processed fibers] The collagen concentration in collagen-processed fibers can be quantified using the method described in Non-Patent Document 1, "Donowaki, 'Quantitative Analysis of Collagen Processed into Fibers,' Fukuoka Prefectural Industrial Technology Center Research Report No. 31, pp. 1-3 (2021)." This method involves reacting hydroxyproline, an amino acid unique to collagen, with chloramine T to convert it to pyrrole, and then reacting it with Ehrlich's reagent to produce a color change.

[0049] [Collagen retention rate of collagen-treated fibers after washing] Furthermore, the collagen-processed fibers of the present invention may have a predetermined wash retention rate. For example, the wash retention rate of the collagen-processed fibers of the present invention can be based on the A-2 method of JIS L0844 (2011) "Test method for color fastness to washing" (5 g / L soap, bath ratio 1:20, 50°C, 30 minutes). This wash retention rate may be set for each type of fiber. The wash retention rate for (fiber type A) may be 60% or more, or 70% or more. The wash retention rate for (fiber type B) may be 85% or more, 90% or more, or 95% or more. The wash retention rate for (fiber type C) may be 90% or more, 92% or more, or 95% or more. [Examples]

[0050] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless its essence is changed.

[0051] [Fibers] The synthetic fibers used were polypropylene (PP), polyester (PET), and nylon (Ny). • PP fiber: Fabric used for dyeing tests by Irozome Co., Ltd. was used. • PET fiber, Ny fiber: A white cloth for color fastness testing was used, in accordance with JIS L 0803 (2011) "Attached white cloth for color fastness testing" of the Japan Standards Association.

[0052] The dry process involved one of the following methods in each test example: "low vacuum plasma treatment," "low-pressure mercury lamp treatment," or "flame treatment."

[0053] • Low vacuum plasma treatment Low-vacuum plasma treatment was performed using the YHS-G gas-introducing vacuum plasma system from Kai Semiconductor Co., Ltd., with surface modification carried out in a 50 Pa vacuum using standard air (Air), nitrogen (N2), and 30% hydrogen (H2) / N2 gas.

[0054] • Low-pressure mercury lamp treatment (ultraviolet treatment and ozone treatment) Surface modification was performed in air at room temperature using Sen Special Light Source Co., Ltd.'s low-pressure mercury lamp power supply UVB-20, which emitted light from their low-pressure UV lamp (20W) UVL20PH-6. This low-pressure mercury lamp treatment involves irradiation with deep ultraviolet light, and it is believed that this irradiation generates ozone.

[0055] • Flame treatment Using Flamebond from Soft99 Corporation, the surface was modified by igniting it in air at room temperature with the maximum gas volume and manually moving it parallel to the fibers.

[0056] • Fiber-collagen interaction and adhesion Collagen (1): The protein used to fix the collagen to the synthetic fiber was "Fish Collagen Peptide SVF" from Asahi Chemical Industries, Ltd. Samples of collagen-processed fibers were prepared by adding fibers to collagen aqueous solutions of various concentrations, treating them at 60°C for 60 minutes, and then washing and drying them.

[0057] • Crosslinking agent Crosslinking agent (1): For crosslinking between the fibers and collagen, "BAYPRET® USV" from Tanatex Chemical Japan Co., Ltd. was used. After treating the fibers with the above collagen aqueous solution, the crosslinking agent was added at room temperature and treated for 20 minutes, then dehydrated and dried to crosslink.

[0058] • Measurement of collagen adhesion The quantification of collagen in fibers was performed using the method described in Non-Patent Document 1, "Donowaki, 'Quantitative Analysis of Collagen Processed into Fibers,' Fukuoka Prefectural Industrial Technology Center Research Report No. 31, pp. 1-3 (2021)." This method involves converting hydroxyproline, an amino acid unique to collagen, to pyrrole by reacting it with chloramine T, and then reacting it with Ehrlich's reagent to produce a color. The amount of fixed collagen was expressed as μg / g-fiber, based on the oven-dry weight of the fiber used for quantification.

[0059] • Washable The washing test was conducted using Method A-2 of JIS L0844 (2011) "Test Method for Color Fastness to Washing" (5 g / L soap, bath ratio 1:20, 50°C, 30 minutes).

[0060] [Test Example 1] [Improvement of collagen interaction by dry process treatment of synthetic fibers] Table 1 shows the effects of dry process treatment conditions on fibers and their interaction with collagen. For all synthetic fibers, dry process treatment improved the interaction between the fiber and collagen compared to the untreated state. The most significant effect was observed with low-vacuum plasma treatment in air for PP. In the untreated state, collagen adhesion was almost zero at 0.1 μg / g-fiber, but after 5 minutes of treatment, it increased to 290 μg / g-fiber, more than 2800 times the amount of collagen that had adhered.

[0061] [Table 1]

[0062] Furthermore, among the fibers shown in Table 1, improvements in collagen content were observed in Ny and PET, indicating that the dry process effect differed depending on the fiber type. Differences in fiber-collagen interaction also existed depending on the gas type; for PP, improvements in collagen content were observed in the order of Air, N2, and 30%H2 / N2, and for PET, in the order of Air and N2. Additionally, differences in adhesion were observed depending on the type of dry process; for PET, collagen content improved in the order of low-vacuum plasma, low-pressure mercury lamp, and flame treatment, as shown in Table 1, and for PP, in the order of low-vacuum plasma and low-pressure mercury lamp. Thus, it became clear that the improvement effect on the interaction between fibers and collagen differs depending on the type of chemical fiber, gas type, and dry process type.

[0063] [Test Example 2] [Improvement of collagen adhesion amount by dry process treatment of synthetic fibers] Table 2 shows the collagen fixation results after low-vacuum plasma treatment and crosslinking of fibers in standard air. These results demonstrate improved collagen fixation after varying the duration of low-vacuum plasma treatment in air for various chemical fibers to enhance the interaction between the fibers and collagen, followed by the crosslinking reaction.

[0064] [Table 2]

[0065] Thus, it was found that the amount of adhesion between fibers and collagen can be improved by the dry process processing time, and that this amount of adhesion can be controlled by time. Furthermore, it was found that even with the same amount of crosslinking agent added, the amount of adhesion can be improved by 3 to 7 times or more under dry process processing conditions. From this, it was shown that fiber-collagen interaction is an important step, and that this is an environmentally friendly processing method that requires less crosslinking agent.

[0066] [Test Example 3] [Improvement of collagen washing durability through dry process treatment of synthetic fibers] Table 3 shows the amount of collagen fixed and the wash retention rate of collagen after crosslinking dry-process treated fibers with collagen and then conducting a washing test. As shown in the table, PET, PP, and Ny showed improved collagen fixation and wash retention rates. This demonstrates that the present invention can improve not only the amount of collagen fixed but also the wash durability of the collagen fixed to the fibers.

[0067] [Table 3]

[0068] [Test Example 4] [Effect of dry process treatment of collagen and / or synthetic fibers on improving fiber-collagen interaction] Table 4 shows the amount of collagen adhering to PP after low-vacuum plasma treatment in various gases. While the amount of untreated collagen adhering to untreated PP was 0.11 μg / g-fiber, indicating almost no adhesion, plasma treatment of collagen with Air, N2, and 30% H2 / N2 improved the fiber-collagen interaction. Furthermore, it was revealed that these interactions improved by plasma treatment of PP in 30% H2 / N2, demonstrating that not only dry process treatment of chemical fibers but also treatment of collagen can influence fiber-collagen interactions.

[0069] [Table 4] [Industrial applicability]

[0070] This invention relates to collagen-processed fibers, which can be used in clothing and other applications and are industrially useful.

Claims

1. The process of treating fibers by a dry process, A method for producing collagen-processed fibers, comprising the step of contacting the fibers treated by the dry process with an aqueous solution containing collagen to fix the collagen contained in the aqueous solution to the fibers, The dry process is one of the processes selected from the group consisting of plasma treatment, ultraviolet treatment, and flame treatment. The aforementioned fiber is one of the fibers selected from the group consisting of polyester, polypropylene, polyethylene, modacrylic, vinylon, nylon, aramid, and polyurethane. A method for producing a crosslinking agent between the fiber and the collagen, wherein the crosslinking agent is a blocked isocyanate crosslinking agent.

2. A process of processing fibers and collagen using a dry process, A method for producing collagen-processed fibers, comprising the step of contacting the fibers processed by the dry process with an aqueous solution containing the collagen processed by the dry process, thereby fixing the collagen contained in the aqueous solution to the fibers, The dry process is one of the processes selected from the group consisting of plasma treatment, ultraviolet treatment, and flame treatment. A method for producing the aforementioned fibers, wherein the fibers are selected from the group consisting of polyester, polypropylene, polyethylene, modacrylic, vinylon, nylon, aramid, and polyurethane.

3. The manufacturing method according to claim 2, wherein the fiber and the collagen are crosslinked with the crosslinking agent for the fiber and the collagen.

4. A method for producing collagen-processed fibers according to any one of claims 1 to 3, wherein the fiber is polyester and the amount of collagen fixed is 57 μg / g-fiber or more.

5. A method for producing collagen-processed fibers according to any one of claims 1 to 3, wherein the fiber is selected from the group consisting of polypropylene, polyethylene, modacryl, and vinylon, and the amount of collagen fixed is 74 μg / g-fiber or more.

6. A method for producing collagen-processed fibers according to any one of claims 1 to 3, wherein the fiber is selected from the group consisting of nylon, aramid, and polyurethane, and the amount of collagen fixed is 38 μg / g-fiber or more.

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