CN110073052B

CN110073052B - Fiber bonded with biologically derived component and method for producing same

Info

Publication number: CN110073052B
Application number: CN201780077266.8A
Authority: CN
Inventors: 泷孝雄
Original assignee: Huanghan Institute Of Pharmaceuticals; Agt & T
Current assignee: Huanghan Institute Of Pharmaceuticals; Agt & T
Priority date: 2016-12-15
Filing date: 2017-03-14
Publication date: 2020-11-03
Anticipated expiration: 2037-03-14
Also published as: WO2018109956A1; EA034593B1; CN110073052A; EA201991462A1

Abstract

The purpose of the present invention is to provide a simple method for chemically bonding a functional substance, particularly a component derived from a living organism, to underwear, clothing, fibers constituting the underwear, clothing, or fibers directly contacting the skin, thereby enabling the addition of the effects thereof. Further, another object is to provide a functional fiber (fiber to which a biologically derived component is bonded) obtained by the method. The functional fiber of the present invention is also required to have excellent washing resistance, and to maintain the added functionality even after several tens of washing. The method of the invention comprises the following steps: a step of bringing the fiber into contact with a dehydration condensation agent solution; and a step of bringing the fiber into contact with a biologically derived component having a carboxyl group or an amino group after the above step, or a method comprising: reacting a biologically derived component having a carboxyl group or an amino group with the dehydration condensation agent solution; and a step of bringing the reaction solution into contact with the fibers, thereby producing fibers having bonded components derived from a living organism.

Description

Fiber bonded with biologically derived component and method for producing same

Technical Field

The present invention relates to a fiber to which a component of biological origin is bonded and a method for producing the same.

Background

The processing of fiber functionality for the purpose of adding a specific function to the fiber is matched. For example, functional fibers having antibacterial, deodorizing, and moisturizing functions are known. These functional fibers are often produced by applying a functional substance such as an antibacterial agent, a deodorant, or a humectant to the fibers and drying the applied substance. However, when these functional substances are attached only to the fiber surface, they are easily detached when washed, and therefore, the processing by this method is not satisfactory in terms of durability.

Therefore, as a method for more efficiently adhering the functional substance, (1) a method of more firmly adhering by using an adhesive or a crosslinking agent in combination (patent document 1: Japanese patent application laid-open No. 7-166469, patent document 2: Japanese patent application laid-open No. 2-300301); (2) a method of bonding a functional substance to a fiber by impregnating the fiber with a processing solution containing a specific hydrolyzed protein, a crosslinking agent and a functional substance, drying the fiber, and then curing a binder by heat treatment (patent document 3: Japanese patent laid-open No. 2000-212874); (3) a method of directly covalently bonding a functional substance to a cellulose-based fiber (patent document 4: international publication No. 2012/067201); (4) a method in which proteoglycan as a functional substance is introduced with a photoreactive group as a substituent and is reacted with fibers under light irradiation (patent document 5: Japanese patent laid-open publication No. 2013-189401), and the like.

However, the method (1) has insufficient adhesion of the functional substance to the fibers and poor washing resistance. In addition, the fiber product obtained by the method (2) has a hard feel when it is in contact with the skin and does not satisfy the feeling of use because the functional substance is attached to the fiber by using the binder. In addition, there is a disadvantage that the washing resistance is insufficient. Further, when the method (3) is used, the types of fibers to which functional substances can be bonded are limited to cellulose fibers and the like, and there is a disadvantage that they cannot be bonded to chemical fibers, animal-derived materials, and the like. (4) The method (2) has a complicated reaction system and cannot be easily carried out.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 7-166469

Patent document 2: japanese laid-open patent publication No. 2-300301

Patent document 3: japanese laid-open patent publication No. 2000-212874

Patent document 4: international publication No. 2012/067201

Patent document 5: japanese patent laid-open publication No. 2013-189401

Disclosure of Invention

Problems to be solved by the invention

Under such circumstances, the present invention has been made to solve the above-mentioned conventional problems, and an object thereof is to provide a simple method for chemically bonding a functional substance, particularly a component derived from a living organism, to underwear, clothing, fibers constituting the underwear, clothing, or fibers directly contacting the skin, thereby enabling the addition of the effects thereof. Further, another object is to provide a functional fiber (fiber to which a biologically derived component is bonded) obtained by the method. The functional fiber of the present invention is also required to have excellent washing resistance, and to maintain the added functionality even after several tens of washing.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have completed the following invention. That is, the gist of the present invention for solving the above problems is as follows.

[1] A method of making a fiber having bonded thereto components of biological origin by comprising: a step of bringing the fiber into contact with a dehydration condensation agent solution; and a step of bringing the fiber into contact with a biologically derived component having a carboxyl group or an amino group after the above step, or a method comprising: reacting a biologically derived component having a carboxyl group or an amino group with the dehydration condensation agent solution; and a step of bringing the reaction solution into contact with the fibers, thereby producing fibers having bonded components derived from a living organism.

[2] The method according to [1], wherein the fiber is dyed with a dye.

[3] The method according to [1] or [2], wherein the fiber is a chemical fiber, a plant fiber or an animal fiber.

[4] The method according to any one of [1] to [3], wherein the biologically derived component is proteoglycan.

[5] The method according to any one of [1] to [4], wherein the proteoglycan is aggrecan.

[6] A fiber to which a component of biological origin is bonded, which is produced by the method according to any one of [1] to [5 ].

[7] A fiber having a biologically derived component bonded thereto, wherein the biologically derived component is chemically bonded to the fiber by a dye component.

[8] A functional clothing formed of the fiber bonded with a component of biological origin according to [6] or [7 ].

[9] A functional bedding formed of the fiber according to [6] or [7] bonded with a component of biological origin.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the method for producing a fiber to which a component derived from a living organism is bonded of the present invention, the component derived from a living organism and various fibers can be chemically bonded easily and safely. In addition, the fiber to which the biogenic component is bonded, which is obtained by the method of the present invention, can be freely produced as fibers to which various functions are added, since the functions of the biogenic component are added to the fibers. As the biogenic component, for example, proteoglycan having an effect of improving moisture retention on the skin may be bonded to the fiber, and the obtained fiber has smooth texture and excellent flexibility, and can provide moisture to the skin of a person wearing the fiber, and can also improve smooth feeling and the like. Further, the above effect is sustained for a long period of time even when the detergent is repeatedly used and washed, and the detergent has excellent washing resistance and durability. Further, although the underwear and stockings made of nylon, acrylic, urethane, or the like are likely to accumulate static electricity during drying due to their properties, an effect of releasing static electricity can be obtained by bonding proteoglycan, and unpleasant feeling due to static electricity in winter can be avoided.

Drawings

FIG. 1 is a graph showing the effect of aggrecan-bonded intimate apparel on atopic dermatitis.

Detailed Description

The present invention will be described in detail below.

Method for producing fiber having bonded biogenic component

The method for producing a fiber having a bonded biogenic component of the present invention comprises: a step of bringing the fiber into contact with a dehydration condensation agent such as a carbodiimide solution; and a step of bringing the fiber into contact with a biologically derived component having a carboxyl group or an amino group after the above step (hereinafter also referred to as "method 1"), or a method comprising: a step of reacting a biologically derived component having a carboxyl group or an amino group with a dehydration condensation agent such as a carbodiimide solution; and a step of bringing the reaction solution into contact with the fiber (hereinafter also referred to as "method 2"), thereby producing a fiber having a biogenic component bonded thereto.

(fiber)

The fibers in the method of the present invention are not particularly limited as long as they are fibers to which the biologically-derived component can be bonded by the method of the present invention, and may be natural fibers or chemical fibers.

Examples of the natural fibers include plant fibers and animal fibers. Examples of the plant fiber include cotton, kapok, hemp, coconut fiber, rush, wheat straw, and the like. Examples of the animal fibers include silk, wool, goat wool, cashmere, mohair, llama hair, horse hair, cow hair, feather fibers, and spider silk.

Examples of the chemical fiber include inorganic fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers. Examples of the inorganic fibers include amorphous fibers such as glass fibers and rock wool; polycrystalline fibers such as carbon fibers and alumina fibers; and single crystal fibers such as wollastonite and potassium titanate fibers. Examples of the regenerated fibers include rayon, high wet modulus viscose (Polynosic), cuprammonium fibers, and chitin and/or chitosan-containing fibers. Examples of the semi-synthetic fibers include acetate, triacetate, and Promix (Promix). Examples of the synthetic fibers include nylon, polyester, acrylic, polyvinyl chloride, vinylon, polypropylene, polyurethane, vinylidene (vinylidene), polyethylene, and polynchelle (polychlal).

The fiber in the method of the present invention is preferably a fiber dyed with a dye or the like, from the viewpoint of ease of bonding of the biologically derived component. The dyed fibers are fibers that are dyed by a conventionally known method that is generally used, depending on the type of the fibers. The dye used for dyeing is not particularly limited, and preferable examples thereof include basic dyes, acid dyes, direct dyes, reactive dyes, disperse dyes, oil-soluble dyes, and fluorescent whitening agents. When the method of the present invention is applied to a fiber to which a dye is chemically bonded, the fiber and a component of biological origin can be indirectly bonded via the dye, and therefore, a desired function can be effectively added to the fiber to which a functional substance is generally difficult to bond (for example, a chemical fiber). Further, it is considered that in the dyeing step, the fibers are treated with a dye and an alkali or an acid, and thus, a state in which the biogenic components are easily bonded is formed.

The form of the fiber in the method of the present invention is not particularly limited as long as it can bond the biogenic component, and examples thereof include primary forms such as raw yarn, silk, tapes, woven fabric, knitted fabric, lace, felt, nonwoven fabric, napped fabric, leather, fur, and the like; and a secondary processed product obtained by further processing the above-mentioned materials. Examples of the secondary processed product include handkerchiefs, towels, wiping cloths, gauze, masks, gloves, panhandles, scarves (scarf), shawl, scarf (muffler), coats, garment sets, uniforms, sweaters, skirts, pants, lappet sweaters, sportswear, men's underwear, men's dress shirts, western-style pajamas, shorts, women's underwear, shorts, underwear, bras, stockings, leg protectors, socks, slippers, bedding-side fabrics, bed sheets, quilt covers, pillowcases, blankets, gloves, and ties.

(component of biological origin)

In the method of the present invention, the component of biological origin means a component of animal or plant origin which can exert a preferable function when bonded to a fiber. In order to be effectively bonded to the fibers by the method of the present invention, it is preferable that the component of biological origin has a carboxyl group or an amino group. Examples of such a biologically derived component include proteoglycan, hyaluronic acid, peptidoglycan, collagen, alginic acid, pectin, fucoidan, heparin, and oligosaccharide peptide. Among them, proteoglycan, collagen, hyaluronic acid and alginic acid are preferable, proteoglycan, collagen and hyaluronic acid are more preferable, and proteoglycan is further preferable. Among proteoglycans, aggrecan is particularly preferred. As these biogenic components, commercially available products can be suitably used.

Proteoglycan, which is a preferred component of biological origin in the method of the present invention, is a generic term for molecules in which 1 or more glycosaminoglycan chains are covalently bonded to a core protein. Glycosaminoglycans to which proteoglycans used in the present invention are bonded are, for example, chondroitin sulfate (chondroitin sulfate), dermatan sulfate (dermatan sulfate), heparan sulfate and keratan sulfate.

Proteoglycan is classified into chondroitin sulfate proteoglycan, dermatan sulfate proteoglycan, heparan sulfate proteoglycan, keratan sulfate proteoglycan, or the like according to the kind of glycosaminoglycan bonded to the core protein. The proteoglycan used in the present invention may be any one of them. Proteoglycans are classified into aggrecan, versican, neuroproteoglycan, brevican, dehydrocholic acid, biglycan, filaggrin, FM, perlecan, syndecan, glypican, photoprotectan, keratin, and the like, based on their origin and function. In the method of the present invention, any of them can be used, but chondroitin sulfate proteoglycan is preferable, and aggrecan is more preferable.

The source of proteoglycan used in the present invention is also not particularly limited, and mammals such as humans, cows, pigs, etc.; birds such as chickens; fishes such as shark and salmon; crustaceans such as crabs and shrimps; and stinging animals such as jellyfish. Among these sources, from the viewpoint of ease of obtaining, moisture retention, and smoothness of the hand when bonded to fibers, proteoglycan derived from mammals such as pigs and fish such as salmon are preferable, proteoglycan derived from fish is more preferable, proteoglycan derived from salmon is particularly preferable, and proteoglycan derived from salmon nasal cartilage is most preferable.

The molecular weight of the proteoglycan used in the present invention is not particularly limited, and can be appropriately set. Preferred proteoglycans have a molecular weight of several tens of thousands to 500 thousands, preferably several hundred thousands to 400 thousands, more preferably 100 to 300 thousands.

In the method of the present invention, the particularly preferred aggrecan among proteoglycans is one of proteoglycans present in a large amount, and is a large-sized keratan sulfate/chondroitin sulfate proteoglycan having a molecular weight of about 2500kDa present in bone tissue. It was shown that the tissue distribution in addition to cartilage was comparatively localized in the brain, aorta, tendon, etc. The molecular weight of the core protein of aggrecan is 210-250 kDa, the core protein has hyaluronic acid bonding capacity, and the core protein and the connexin form a huge complex together with hyaluronic acid. Through the large number of glycosaminoglycan chains bonded to the core protein, a highly hydrated gel is formed, which fills the space, thereby giving mechanical strength to the cartilage tissue.

The purity of the aggrecan in the present invention is preferably 95.0% or more, more preferably 97.0% or more, and still more preferably 99.0% or more, as determined by analysis using HPLC. The purity of the aggrecan in the present invention can be calculated from the peak area of HPLC. The aggrecan of the present invention is obtained by using aggrecan having improved purity by reducing inclusion contamination by extraction from a thin sheet of cartilage or by reducing the inclusion to the limit by a desired measure with respect to the concentration of citric acid used for extraction, extraction time, and the like, instead of using a material obtained by cutting cartilage as a material in the production process as in the conventional art, and thus the fiber produced by the method of the present invention can maintain the skin well both at the time of wearing and after wearing, has excellent moisture retention properties, and can improve the tension and smoothness of the skin.

(dehydration condensation agent)

The dehydration condensation agent in the present invention is a reaction reagent for synthesizing a carboxylic acid derivative such as an ester or amide by an addition elimination reaction. As such a dehydration condensation agent, a carbodiimide having a functional group of-N ═ C ═ N —, is preferable, and specific examples thereof include water-soluble carbodiimides (WSC HCl: 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride), N '-Dicyclohexylcarbodiimide (DCC), diphenylphosphoryl azide (DPPA), Carbonyldiimidazole (CDI), O- (7-azabenzotriazol-1-yl) -N, N', -tetramethylurea cationic Hexafluorophosphate (HATU), and the like. Among them, a water-soluble and easily handled dehydration condensation agent such as a water-soluble carbodiimide is preferable. If necessary, 1-hydroxy-1H-benzotriazole monohydrate (HOBt. H) may be added₂O), 4-Dimethylaminopyridine (DMAP), N-diisopropylethylamine, and the like.

The method of the present invention will be specifically described below.

(method 1)

The method 1 is a method for producing a fiber to which a biologically-derived component is bonded by a method including the step (i) of contacting a fiber with a dehydration condensation agent solution and the step (ii) of contacting a fiber with a biologically-derived component having a carboxyl group or an amino group after the step (i).

In step (i), the fiber is washed with water, a detergent, or the like in advance and then immersed in a carbodiimide solution. The dehydration condensation agent solution is produced by adding a dehydration condensation agent to water.

The concentration of the dehydration condensation agent (e.g., carbodiimide solution) is 0.01 to 0.5M, preferably 0.05 to 0.2M, and more preferably 0.1 to 0.1M. Further, when the reaction is carried out using a dehydration condensation agent (for example, a carbodiimide compound), HOBt (1-hydroxybenzotriazole) as a catalyst may be used. The reaction conditions for activation with the dehydration condensation agent (e.g., carbodiimide compound) are not particularly limited as long as the reaction conditions are such that the fibers themselves or the dye substance bonded to the fibers are activated with the dehydration condensation agent (e.g., carbodiimide compound). The reaction temperature when the fiber is immersed in a dehydration condensation agent (e.g., carbodiimide) solution is 0 to 60 ℃, preferably room temperature to 50 ℃, and more preferably room temperature to 40 ℃. The reaction time is not limited as long as the fiber is not damaged, and is, for example, 30 minutes to 24 hours, preferably 30 minutes to 2 hours, and more preferably 30 minutes to 1 hour.

The fibers are immersed in a dehydration condensation agent (for example, carbodiimide) solution, sufficiently wrung, or washed with water or the like, and then transferred to the next step (ii).

In the step (ii), the fiber is brought into contact with a biologically derived component having a carboxyl group or an amino group after the step (i). That is, the fiber after the step (i) is immersed in a solution containing a component of biological origin.

The concentration of the solution containing the component of biological origin may be 0.01 to 50% by mass, 0.1 to 10% by mass, preferably 0.5 to 5% by mass, more preferably 0.5 to 1.5% by mass. The reaction temperature when the fiber is immersed in a solution containing a component of biological origin is 0 to 60 ℃, preferably room temperature to 50 ℃, and more preferably room temperature to 40 ℃. The reaction time is 30 minutes to 48 hours, preferably 2 hours to 36 hours, more preferably 4 hours to 24 hours.

The fiber to which the component derived from a living organism is bonded can be produced by immersing the fiber in a solution containing the component derived from a living organism, washing the immersed fiber with water, and drying the washed fiber.

In the step (ii), the solution containing the biologically-derived component is immersed, sufficiently wrung, and the steps (i) and (ii) are repeated again, whereby the amount of the biologically-derived component bonded to the fiber can be increased. In this case, the amount of the biologically derived component bonded to the fiber itself may be increased, or the biologically derived component may be further bonded to the biologically derived component bonded to the fiber, so that the biologically derived component may be present in 2 or more layers. Such a structure having 2 or more layers can be obtained by linking the carboxyl group of the component of biological origin already present on the fiber product and the amino group of the component of biological origin to be further added, or by linking the amino group of the component of biological origin already present on the fiber product and the carboxyl group of the component of biological origin to be further added. The step of further bonding the biogenic component to the biogenic component layer may be repeated until a desired quality is obtained. In this way, when the treatment of bonding the biogenic component to the fiber is repeated 1 or more times (preferably, a plurality of times), a fiber product in which all layers of the biogenic component are bonded is obtained, and the fiber product has a more excellent hand feeling than the case of bonding the biogenic component 1 time, and can effectively exert a function of providing moisture to the skin.

(method 2)

The method 2 is a method for producing a fiber to which a biologically-derived component is bonded, by a method including the step (iii) of reacting a biologically-derived component having a carboxyl group or an amino group with a dehydration condensation agent solution and the step (iv) of bringing the reaction solution into contact with the fiber.

In the step (iii), a dehydration condensation agent such as a carbodiimide compound is added to and mixed with a solution containing a biologically derived component having a carboxyl group or an amino group to activate the carboxyl group, the amino group, or the hydroxyl group of the biologically derived component. The temperature during the mixing is 0 to 50 ℃, preferably room temperature to 50 ℃, and more preferably room temperature to 40 ℃. The process may be carried out immediately after the mixing in the step (iv), or the mixture may be mixed for about 30 seconds to 30 minutes before the process is carried out in the step (iv). In addition, the step (iii) and the step (iv) may be performed simultaneously. That is, the fiber may be immediately impregnated in a solution containing a biologically derived component having a carboxyl group or an amino group, to which a dehydration condensation agent (e.g., carbodiimide) is added.

The concentration of the solution containing the biologically derived component having a carboxyl group or an amino group may be 0.01 to 50% by mass, 0.1 to 10% by mass, preferably 0.5 to 5% by mass, and more preferably 0.5 to 1.5% by mass.

The amount of the dehydration condensation agent (e.g., carbodiimide compound) added is an amount to give a final concentration of 0.01 to 0.5M, preferably 0.05 to 0.2M, and more preferably 0.1 to 0.1M. Further, HOBt (1-hydroxybenzotriazole) may be added as a catalyst.

In the step (iv), the reaction solution (mixed solution) produced in the step (iii) is brought into contact with the fibers. That is, the reaction solution (mixed solution) is immersed in the fiber to which the biogenic substance is to be bonded.

The fiber washed with water or the like is immersed in a solution containing a component of biological origin. The reaction temperature in this case is 0 to 60 ℃, preferably room temperature to 50 ℃, and more preferably room temperature to 40 ℃. The reaction time is 30 minutes to 48 hours, preferably 2 hours to 36 hours, more preferably 4 hours to 24 hours. Then, the fiber to which the biogenic component is bonded can be produced by sufficiently washing with water and drying.

In the step (iv), the solution containing the biologically-derived component is immersed, sufficiently wrung, and the steps (iii) and (iv) are repeated again, whereby the amount of the biologically-derived component bonded to the fiber can be increased. In this case, the amount of the biologically derived component bonded to the fiber itself may be increased, or the biologically derived component may be further bonded to the biologically derived component bonded to the fiber, so that the biologically derived component may be present in 2 or more layers. Such a structure having 2 or more layers can be obtained by linking the carboxyl group of the component of biological origin already present on the fiber product and the amino group of the component of biological origin to be further added, or by linking the amino group of the component of biological origin already present on the fiber product and the carboxyl group of the component of biological origin to be further added. The step of further bonding the biogenic component to the biogenic component layer may be repeated until a desired quality is obtained. In this way, when the treatment of bonding the biogenic component to the fiber is repeated 1 or more times (preferably, a plurality of times), a fiber product in which all layers of the biogenic component are bonded is obtained, and the fiber product has a more excellent hand feeling than the case of bonding the biogenic component 1 time, and can effectively exert a function of providing moisture to the skin.

By the method of the present invention, it is possible to chemically bond a component derived from a living organism to various fibers in a simple manner. In addition, according to the method of the present invention, the obtained fiber to which the biologically derived component is bonded can be arbitrarily produced by adding various functions to the fiber because the function of the biologically derived component is added to the fiber. As the biogenic component, for example, proteoglycan having an effect of improving moisture retention on the skin may be bonded to the fiber, and the obtained fiber has smooth texture and excellent flexibility, and can provide moisture to the skin of a person wearing the fiber, and can also improve smooth feeling and the like. Further, the above effect is sustained for a long period of time even when the detergent is repeatedly used and washed, and the detergent has excellent washing resistance and durability. In addition, the method of the present invention does not require the use of dangerous chemicals, and therefore is highly safe.

The progress of the reaction when the biologically derived component is bonded to the fiber by the method of the present invention can be confirmed, for example, by the following method. That is, the reaction rate, reaction conditions, and the like can be confirmed by quantifying the amount of the biologically-derived component such as aggrecan used for bonding to the fiber.

In the case where the biologically-derived component is aggrecan, the progress of the reaction and the residual amount of aggrecan can be determined by quantification of uronic acid using the carbazole sulfuric acid method based on the Bitter-Muir method.

Specifically, a part of the aggrecan solution before the reaction is collected. Subsequently, after the condensing agent and the fibers were reacted, the fibers were immersed in the aggrecan solution, and a portion (about 1 mL) was collected from the reaction solution at every certain time. The collected samples were diluted 10-fold, 50-fold, 100-fold, 500-fold, 1000-fold. 1mL of each of the dilutions was collected, and 5mL of 0.25M sodium borate concentrated sulfuric acid solution was added. After sufficiently stirring, 0.2mL of 0.125% carbazole/ethanol solution was added thereto, the mixture was sufficiently stirred, and the mixture was heated in a boiling water bath for color development for 15 minutes, and then absorbance at 530nm was measured. As the standard solution, 10, 20, 30, 50, and 100. mu.g of glucuronic acid was dissolved in 1mL of the solution. Even when the amount of aggrecan (residual amount) in the sample is constant as converted from the glucuronic acid concentration, an estimate of the maximum amount of aggrecan-to-fiber bonding under the conditions can be calculated from the residual amount. In addition, by this method, more appropriate reaction conditions for bonding aggrecan to the fiber can be selected. If the aggrecan remaining in the reaction solution can be sufficiently recovered, the recovered aggrecan can be used repeatedly for the 2 nd and subsequent reactions.

As a method for measuring the amount of the biologically derived component bonded to the fiber, a method suitable for each biologically derived component can be appropriately selected and applied. For example, when the biologically derived component is aggrecan, the amount of aggrecan bound to the fibers can be calculated by treating the fibers to which aggrecan is bound with an enzyme and quantifying the amount of chondroitin sulfate released.

< fibers bonded with components of biological origin >

The present invention also includes a fiber having a bio-derived component bonded thereto obtained by the method for producing a bio-derived component bonded fiber of the present invention. The fiber to which the biologically derived component is bonded of the present invention is produced by the above production method, whereby the biologically derived component and the fiber are chemically bonded to add a function possessed by the biologically derived component. The fiber bonded with the bio-derived component of the present invention forms a structure in which the bio-derived component having a carboxyl group or an amino group is chemically bonded to the fiber by the dye component.

Since the fiber to which the biologically derived component is bonded according to the present invention has a function of adding the biologically derived component to the fiber, the fiber having various functions can be formed depending on the bonded biologically derived component. As the biogenic component, for example, proteoglycan having an effect of improving moisture retention to the skin may be used, and the obtained fiber has a smooth hand and excellent flexibility, and can provide moisture to the skin of a person wearing the fiber, and can also improve smoothness and the like. Further, the above effect is sustained for a long period of time even when the detergent is repeatedly used and washed, and the detergent has excellent washing resistance and durability.

Specific examples of products (functional clothing, functional bedding, and the like) using the biogenic component-bonded fiber of the present invention include primary processed forms such as raw yarn, silk, tapes, woven fabric, knitted fabric, lace, felt, nonwoven fabric, pile fabric, leather, fur, and the like; and a secondary processed product obtained by further processing the above-mentioned materials. Examples of the secondary processed product include handkerchiefs, towels, wiping cloths, gauze, masks, gloves, panhandles, scarves (scarf), shawl, scarf (muffler), coats, garment sets, uniforms, sweaters, skirts, pants, lappet sweaters, sportswear, men's underwear, men's dress shirts, western-style pajamas, shorts, women's underwear, shorts, underwear, bras, stockings, leg protectors, socks, slippers, bedding-side fabrics, bed sheets, quilt covers, pillowcases, blankets, gloves, and ties.

The biologically derived component-bonded fiber of the present invention having proteoglycan, particularly aggrecan, bonded to a biologically derived component can also expect troublesome effects of improving skin with respect to the contacted skin by the EGF action possessed by aggrecan. For example, the present invention can be applied to clothing such as underwear made from the fiber having a biogenic component bonded thereto of the present invention, in which improvement of symptoms is expected for atopic dermatitis patients and patients suffering from bedsores.

Examples

The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. Unless otherwise specified, (%) is expressed in terms of mass%.

[ production of proteoglycan-bonded fiber ]

< example 1 >

4 pairs of tights (commercially available, camel, nylon or polyurethane as raw material) were washed with detergent gently. The tights were immersed in 1L of a carbodiimide solution to which 3mL of water-soluble carbodiimide was added for 30 minutes to 1 hour. The temperature was set at room temperature to 50 ℃. Fully wringing and dipping in 1L of 0.5-1% proteoglycan solution. The temperature was set to room temperature to 40 ℃ and left overnight. After sufficient squeezing, the fiber is immersed in the same carbodiimide solution for 30 to 60 minutes. After sufficient squeezing, the mixture is dipped in 0.5-1% proteoglycan solution and left for one night. This operation was repeated 3 to 4 times. Finally the briefs are thoroughly washed with water and dried. Proteoglycan (aggrecan) manufactured by Institute Glycosmo co.ltd. was used as proteoglycan. The same applies to the following examples.

< example 2 >

3mL of water-soluble carbodiimide was added to 1L of 0.5-1% proteoglycan solution, and stirred at room temperature to 40 ℃ for 30 minutes. 4-pair pantyhose (commercially available, camel or black, nylon or polyurethane as a raw material) which were previously washed with a detergent was immersed in the liquid. After being placed at room temperature overnight, the mixture was sufficiently wrung out. This operation was repeated 3 to 4 times. And finally, taking out the stockings, fully washing with water and drying.

< example 3 >

Adding 3mL of water-soluble carbodiimide into 1L of 0.5-1% proteoglycan solution, and stirring for 1-2 minutes at room temperature-40 ℃. 4-pair pantyhose (commercially available, camel or black, nylon or polyurethane as a raw material) which were previously washed with a detergent was immersed in the liquid. After being placed at room temperature overnight, the mixture was sufficiently wrung out. This operation was repeated 3 to 4 times. And finally, taking out the stockings, fully washing with water and drying.

< example 4 > (bonding of proteoglycan to Silk fiber intimate apparel)

The silk fiber intimate apparel (commercially available, white) was washed with water in advance. The intimate apparel was immersed in a water-soluble carbodiimide solution (a solution prepared by adding 3mL of water-soluble carbodiimide to 1L of water) at room temperature to 40 ℃ for 1 hour. Squeezing was performed sufficiently to remove excess carbodiimide solution. The body suit was then dipped in a 1% proteoglycan solution and placed at room temperature to 40 ℃ at first evening. After fully wringing, the mixture is immersed in a carbodiimide solution for 1 hour at room temperature to 40 ℃. After squeezing sufficiently, the tube was immersed in a 1% proteoglycan solution and placed at evening. And (3) repeating the operations of treating the carbodiimide solution and treating the proteoglycan solution for 1-2 times, and then fully washing and drying the close-fitting clothes.

< example 5 > (bonding of proteoglycan to kapok fiber intimate apparel)

The kapok fiber intimate apparel (commercial, black) was previously water-washed. The intimate apparel was immersed in a water-soluble carbodiimide solution (a solution prepared by adding 3mL of water-soluble carbodiimide to 1L of water) at room temperature to 40 ℃ for 1 hour. Squeezing was performed sufficiently to remove excess carbodiimide solution. The body suit was then dipped in a 1% proteoglycan solution and placed at room temperature to 40 ℃ at first evening. After fully wringing, the mixture is immersed in a carbodiimide solution for 1 hour at room temperature to 40 ℃. After squeezing sufficiently, the tube was immersed in a 1% proteoglycan solution and placed at evening. And (3) repeating the operations of treating the carbodiimide solution and treating the proteoglycan solution for 1-2 times, and then fully washing and drying the close-fitting clothes.

< example 6 > (binding of proteoglycan to woolen scarf)

The same procedure as in example 4 or 5 above was carried out for a woolen scarf (commercially available, brown).

< example 7 > (bonding of proteoglycan to Men's long-sleeved underwear)

3mL of water-soluble carbodiimide was added to 1L of a 1% proteoglycan solution and mixed thoroughly, and the semidry men's long-sleeved underwear (commercially available product, white, raw material: 57% acrylic, 38% rayon, 5% polyurethane) which had been washed with water in advance was permeated sufficiently. Then, the bag was wrapped with Saran Wrap (registered trademark) and allowed to stand at room temperature for one day while preventing the entry of air. After washing with sufficient water to remove carbodiimide and unbound proteoglycan, the shady part is dried.

[ surveyor's review ]

Critics investigated the proteoglycan conjugates (tights, panty stockings, silk fiber underwear, kapok fiber underwear, woolen scarves, chemical fiber underwear) produced in examples 1 to 7 above. Specifically, each product was administered to a plurality of subjects for 2 weeks to 1 month. Meanwhile, as a control, the same samples (comparative examples 1 to 6) without proteoglycan were used for comparison. The results of questionnaire were collected in the following table. The evaluation criteria are as follows.

For each evaluation item, 4 ratings of 1 to 4 were performed, and the average value for all the commentators is shown in the following table.

1: is not suitable for

2: is slightly suitable

3: is suitable for

4: is too suitable

[ Table 1]

[ Table 2]

As shown in tables 1 and 2, the proteoglycan-bonded products were softer in fiber, milder to the skin, excellent in dry feeling, and pleasant to wear as compared with the comparative examples as a whole. In addition, the skin was evaluated to be smooth and moist after wearing, and the moisturizing effect was obtained. Therefore, it is found that the product of the present invention has an effect of using a cosmetic exhibiting a moisturizing effect or the like by chemically bonding proteoglycan and fiber. These products also exhibited similar effects even after washing 20 times or more by a usual method.

In addition to the above evaluation items, the stockings of examples also exhibited the effect of being less likely to generate static electricity than the comparative examples.

< example 8 > (comparison of non-dyed fiber and dyed fiber)

The towel dyed with the dye and the unprocessed towel not dyed (commercially available, raw material is cotton 100%) were washed with a detergent in advance with light water. These towels were immersed in 1L of a carbodiimide solution containing 3mL of a water-soluble carbodiimide for 30 minutes to 1 hour. The temperature was set at room temperature to 50 ℃. Fully wringing and dipping in 1L of 0.5-1% proteoglycan solution. The temperature was set to room temperature to 40 ℃ and left overnight. After sufficient squeezing, the fiber is immersed in the same carbodiimide solution for 30 to 60 minutes. After sufficient squeezing, the mixture is dipped in 0.5-1% proteoglycan solution and left for one night. This operation was repeated 3 to 4 times. And finally, fully washing and drying the towel.

The obtained towel was confirmed to be used by a reviewer, and the following results were obtained. That is, the towel dyed with the dye had smooth hand feeling by bonding proteoglycan, and the hand skin after use had wet feeling. And this effect continues even if the washing is performed multiple times. On the other hand, in the case of the unprocessed towel, the hand feeling becomes smooth by the bonding of proteoglycan, and the hand skin feeling after use feels moist, but such an effect disappears in advance by repeated washing.

EXAMPLE 9 (Effect of aggrecan-bonded intimate apparel on living bodies (blood flow improvement))

Healthy adult men (43 years) were used as subjects. After keeping the skin quiet for 10 minutes at room temperature of 25.2 ℃ and humidity of 47%, the blood flow rate and blood flow volume were measured by a laser doppler flow meter for 20 minutes while the skin was lying on the back with the unworn intimate clothing. After 20 minutes of rest, the underwear with the aggrecan bonded thereto was worn, and the blood flow rate and blood flow volume were measured by a laser doppler blood flow meter for 20 minutes in the same manner as in the lying state. The blood flow rate and the rate of change in blood flow with respect to the case of wearing the aggrecan-bonded body suit when wearing the raw body suit are as follows.

Blood flow rate 0.97 times (3.0% reduction)

Blood flow 1.10 times (11% increase)

When the aggrecan-bonded body suit was worn, a 3% reduction in blood flow rate was found compared to when the raw body suit was worn. This is thought to be due to vasodilation by the sole action of the aggrecan-bonded fabric. On the other hand, when the aggrecan-bonded body suit was worn, the blood flow rate was increased by 11% as compared with when the raw body suit was worn, and the effect of improving blood flow by wearing the aggrecan-bonded body suit was found.

EXAMPLE 10 > (Effect of aggrecan-bonded intimate apparel on atopic dermatitis)

A 16-year-old man showing symptoms of atopic dermatitis was taken as a subject. The subject showed itching of the back, abdomen, and arms and eczema due to atopic dermatitis, and as a result, the subject was coated with an antihistamine, a steroid agent, a humectant, and the like, but did not find much improvement in itching and the like. Therefore, the effect of the close-fitting clothes having aggrecan bonded thereto on atopic dermatitis was investigated.

The test subjects alternately worn 3 colored T-shirts (2 black and 1 gray) with aggrecan-bonded cotton, and found that eczema and itching of the back and abdomen were relieved. In winter season with low temperature and dry air, the arms of the wearer were seriously affected by eczema and itching due to wearing of the commercially available long-sleeved underwear (fig. 1, a). Therefore, wearing 2 pieces of colored long-sleeved underwear (black, polyester 60%, cotton 35%, polyurethane 5%) with aggrecan bonded alternately, the eczema of the arms was calmed and the itching was suppressed for 2 weeks (fig. 1B). Further, after 2 weeks, eczema still subsided.

It is thus found that the close-fitting garment to which aggrecan is bonded has an effect of improving the symptoms of atopic dermatitis and a therapeutic effect.

Industrial applicability

According to the method for producing a fiber to which a component derived from a living organism is bonded of the present invention, the component derived from a living organism and various fibers can be chemically bonded easily and safely. In addition, the fiber to which the biologically derived component is bonded, which is obtained by the method of the present invention, can be freely produced as fibers to which various functions are added, because the functions of the biologically derived component are added to the fibers. As the biogenic component, for example, proteoglycan having an effect of improving moisture retention on the skin may be bonded to the fiber, and the obtained fiber has smooth texture and excellent flexibility, and can provide moisture to the skin of a person wearing the fiber, and can also improve smooth feeling and the like. In particular, garments such as underwear to which aggrecan is bonded are suitably used as functional underwear (functional garments) because they have an effect of improving blood circulation of a person wearing the garment and an effect of improving and treating atopic dermatitis. Further, the fiber of the present invention has the above-described effects for a long period of time even when repeatedly used and washed, and has excellent washing resistance and durability.

Claims

1. A method of making a fiber having bonded thereto components of biological origin by comprising: contacting the fiber dyed with the dye with a dehydration condensation agent solution; and

a method comprising a step of bringing the fibers into contact with a biologically derived component having a carboxyl group or an amino group after the step,

or

By including: reacting a biologically derived component having a carboxyl group or an amino group with the dehydration condensation agent solution; and

a method comprising the step of bringing the reaction solution into contact with a fiber dyed with a dye,

thereby producing a fiber bonded with a component of biological origin.

2. The method of claim 1, wherein the fibers are chemical, vegetable, or animal fibers.

3. The method of claim 1 or 2, wherein the component of biological origin is proteoglycan.

4. The method of claim 3, wherein the proteoglycan is aggrecan.

5. A fiber bonded with a component of biological origin produced by the method of claim 1 or 2.

6. The fiber to which biogenic components are bonded according to claim 5, wherein at least one biogenic component selected from the group consisting of proteoglycan, collagen and hyaluronic acid is chemically bonded to the fiber by means of a dye component.

7. The biogenic component-bonded fiber of claim 6, wherein said proteoglycans are aggrecan.

8. The fiber bonded with a biologically derived component according to any one of claims 5 to 7, which is used for at least one use selected from the group consisting of moisturizing use, antistatic use, skin inflammation improvement use and blood flow improvement use.

9. A functional clothing article comprising the fiber to which a component derived from a living organism is bonded according to any one of claims 5 to 8.

10. The functional clothing according to claim 9, which is used for at least one use selected from the group consisting of moisturizing use, antistatic use, skin inflammation improvement use, and blood flow improvement use.

11. A functional bedding comprising the fiber to which a component derived from a living organism is bonded according to any one of claims 5 to 8.

12. The functional bedding according to claim 11, which is used for at least one use selected from the group consisting of moisturizing use, antistatic use, skin inflammation improvement use, and blood flow improvement use.