JP2007224429A - Contact cold-sensation fiber and fiber treating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a soft contact cold-sensation fiber producible by post-processing of a yarn or a woven fabric, having excellent contact sold-sensation properties and water resistance, scarcely yellowing and having a good touch feeling and to provide a fiber treating agent for producing the contact cold-sensation fiber. <P>SOLUTION: The contact cold-sensation fiber is obtained by fixing a functional component composed of at least one kind of protein derived from mucopolysaccharides and silk to the fiber surface with a binder. A silicone emulsion as a binder base and a polyethylene glycol diglycidyl ether as a cross-linking agent are contained in the binder. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a contact-cooled fiber that gives a cold feel when touched, and a fiber treatment agent for use in the production thereof.

  Conventionally, in order to make the functions of various fibers feel, texture, moisture retention, gloss, etc. more natural, proteins such as silk fibroin and sericin contained in natural silk, hyaluronic acid contained in animal skin, etc. A technique for attaching mucopolysaccharide to fibers as a functional component is known. If natural silk components are attached to the fibers, the touch, gloss, silk scrub sound, etc. can be made to resemble natural silk. Moreover, moisture adhesion and moisture absorption can be imparted to the fiber by attaching mucopolysaccharide to the fiber.

  For example, in Patent Document 1, a silk-derived protein such as sericin is mixed with a hydrophilic polymer such as polyether-modified silicone polymer, polyether, polyglycerin ester, alkynolamide, and physically adhered to the fiber surface. The technology is described. It is described that if fibers are treated with this fiber treatment agent, the contradicting properties of liquid permeability, durable hydrophilicity, and wettability can be maintained in a well-balanced manner, and the fabric can be made soft and gentle to the skin. .

Further, in paragraph No. 0017 of Patent Document 2, a reaction composition of a fish scale-derived collagen oligopeptide and oligochitosan is attached to a fiber with a fiber treatment agent mixed with a urethane-based binder having a plurality of isocyanate groups. It describes that it can be made into a fiber having moisture retention and antibacterial properties.
Furthermore, in paragraph numbers 0021 to 0025 of the same document, the same effect can be obtained by using a copolymer of an acrylic monomer and an organosilicon compound monomer (trade name “Light Spock S-60NF” manufactured by Kyoeisha Chemical Co., Ltd.) as a binder. It is described that it can be made into the fiber which plays.

  Patent Document 3 discloses a fiber treatment in which silk fibroin or hydrolyzed collagen is attached to fibers using a crosslinking agent having a plurality of isocyanate groups, a crosslinking agent having a plurality of aldehyde groups, or an ethyleneimine-based crosslinking agent. Agents have been proposed. By treating the fiber with this fiber treatment agent, proteins and mucopolysaccharides derived from natural products can be attached to the fiber, and functions such as antibacterial, deodorant, anti-inflammatory, antiallergic, moisturizing, and whitening are imparted. It is described that it can.

  On the other hand, as the contact cooling sensation fiber having the contact cooling sensation which gives a cold feeling when touching the fiber, the following are known. (1) A cold-textured woven fabric in which ethylene vinyl alcohol fibers are blended with polyester fibers. (2) Cold-textured woven fabric using rayon fibers that knead polymer microcapsules that cause phase changes at body temperature and take away latent heat (3) Cold kneaded special inorganic particles with high thermal conductivity in nylon polymer Sensitive woven fabric.

JP, 2004-25828, A Claim 4 JP, 2004-308063, A paragraph numbers 0017, 0021-0025 Japanese Patent Laid-Open No. 2000-212874

  However, functional fibers using functional components such as the above-mentioned conventional mucopolysaccharides and silk-derived proteins are known for functional fibers with functions such as moisture retention, water absorption, antibacterial properties, texture, and touch. However, there are no known contact-cooled fibers that give a cold feel when touched.

Moreover, the functional fiber processed with the said fiber processing agent has the following faults.
That is, in the fiber treatment agent of Patent Document 1, a hydrophilic protein derived from silk such as sericin is simply physically mixed with a hydrophilic polymer such as a polyether-modified silicone polymer or polyether. Since it is not chemically bonded to the polymer, it is inferior in water resistance, and the silk-derived protein may flow out of the fiber by washing.

  Further, it is a fiber treatment agent for adhering a reaction composition of a fish scale-derived collagen oligopeptide and oligochitosan described in Patent Document 2 to a fiber using a copolymer of an acrylic monomer and an organosilicon compound monomer as a binder. However, it is only physical mixing, and it is also inferior in water resistance, and there exists a possibility that the reaction composition of a collagen oligopeptide and oligo chitosan may flow out of a fiber by washing.

In this regard, if the urethane-based binder having an isocyanate group described in Patent Document 2 is used, the amino group or carboxylic acid group of collagen and the isocyanate group of the urethane-based binder are chemically bonded. It can be a functional fiber.
In addition, a crosslinking agent (that is, a crosslinking agent having a plurality of isocyanate groups, a crosslinking agent having a plurality of aldehyde groups, or an ethyleneimine-based crosslinking agent) used in the fiber treatment agent described in Patent Document 3 is used. Even if it uses, it can be set as the functional fiber excellent in water resistance similarly. This is because these cross-linking agents chemically bond with amino groups and carboxylic acid groups of silk fibroin and hydrolyzed collagen.
However, in these fiber treatment agents, in order to bind functional components such as silk fibroin and hydrolyzed collagen to the binder base, it is necessary to modify the functional group that chemically bonds to the functional component in the binder base. For this reason, the degree of freedom in selecting the binder base is small, and it is difficult to freely select a binder base that is excellent in water resistance, hardly yellows, is soft and has a good texture.

  On the other hand, a cold feeling woven fabric blended with the above-mentioned ethylene vinyl alcohol fiber and polyester fiber, a cold sensation woven fabric using rayon fibers kneaded with polymer microcapsules that cause phase change at body temperature and take away latent heat, nylon In the case of contact cooling sensation fibers in which special inorganic particles having high thermal conductivity are kneaded in a polymer, special fibers having a cooling sensation effect must be produced in advance before forming a woven fabric. For this reason, compared with the contact cooling sensation fiber which gives the cooling sensation effect by post-processing with respect to the existing versatile thread | yarn and textile fabric, a manufacturing process becomes complicated and manufacturing cost becomes high. In addition, the cooling effect is not so good, and there is a disadvantage that the washing durability is inferior.

  The present invention has been made in view of the above-described conventional circumstances, and can be manufactured by post-processing yarns and fabrics, has excellent contact cold sensitivity, excellent water resistance, hardly yellowed, and is soft. It is a problem to be solved to provide a contact-cooled fiber having a good texture and a fiber treatment agent for producing such a contact-cooled fiber.

  As a result of conducting intensive research to solve the above problems, the inventors have developed a functional component in a polymer that is easily entangled with fibers as a method of immobilizing functional components such as mucopolysaccharides and silk-derived proteins on fibers. Rather than fixing directly by chemical bonding, the inventors found that the above problems can be solved if the functional component is indirectly bonded to the polymer that is easily entangled with the fiber using a crosslinking agent, and the present invention has been completed. It was.

That is, the contact cooling sensation fiber of the present invention has a functional component consisting of at least one of mucopolysaccharide and silk-derived protein fixed to the fiber surface by a binder,
The binder includes a binder base made of a polymer, a functional group of the binder base, and a cross-linking agent having a plurality of functional groups capable of forming a cross-linked structure by chemically bonding with the functional component. Is included.

  In the contact-cooled fiber of the present invention, a functional component composed of at least one of mucopolysaccharide and silk-derived protein is fixed to the fiber surface by a binder composed of a binder base and a crosslinking agent. Since the cross-linking agent has a plurality of functional groups that can be chemically bonded to both the binder base made of a polymer and the functional component, it must be chemically bonded to both the functional component and the binder base. Can do. For this reason, unlike the case where the functional component is physically mixed in a binder base composed of a simple polymer, the functional component is not easily detached from the binder base and has excellent water resistance.

  In addition, since the functional component is indirectly bonded to the binder base via the crosslinking agent, it is not necessary to modify the functional group that chemically bonds to the functional component on the binder base. For this reason, the degree of freedom in selecting the binder base is increased, and it is possible to select a binder base that has excellent water resistance, is resistant to yellowing, is soft, and has a good texture.

  Furthermore, according to the test results of the inventors, the contact cooling sensation fiber of the present invention has only characteristics such as moisture retention and hygroscopicity, which are conventionally known for functional fibers to which mucopolysaccharide and silk-derived protein are attached. In addition, it has an excellent function of giving a cold feel when touched.

  Further, the contact cooling sensation fiber of the present invention can be produced by post-processing a yarn or a woven fabric, and it is not necessary to use a special yarn or woven fabric, and can be applied to any type of yarn or woven fabric. can do. For this reason, the manufacturing cost is also low.

  Therefore, the contact cooling sensation fiber of the present invention can be produced by post-processing a yarn or a woven fabric, and is a contact cooling sensation fiber that is excellent in water resistance, hardly yellowed, is soft and has a good texture.

  In the contact cooling sensation fiber of the present invention, the type of fiber is not particularly limited, and any of synthetic fibers such as polyester, rayon and nylon, and natural fibers such as cotton and hemp can be applied. The mucopolysaccharide is not particularly limited, and examples thereof include hyaluronic acid, chondroitin, and a mixture thereof. Furthermore, examples of silk-derived proteins include silk fibroin, sericin, and mixtures thereof.

The cross-linking agent preferably has at least one of an epoxy group and an alkoxysilyl group as a functional group. If the crosslinking agent has an epoxy group as a functional group, it can be easily chemically bonded to an amino group or a carboxylic acid group present in a mucopolysaccharide or silk-derived protein. In addition, since there are a large number of functional groups bonded to the epoxy group, the degree of freedom in selecting as a binder base is increased. For this reason, it is possible to select from among a large number of binder bases that are excellent in water resistance, hardly yellowed, are soft and have a good texture.
Examples of the crosslinking agent having an epoxy group as a functional group include those obtained by modifying an epoxy group with a polyhydric alcohol such as polyethylene glycol, polypropylene glycol, sorbitol, polyglycerol, diglycerol, glycerol, and 1,6-hexanediol. It is done. Also, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, triglycidyl-tris (2-hydroxyhexyl) isocyanurate, glycerol polyglycidyl ether, trimethylol Propane polyglycidyl ether, resorcin diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, adipic acid diglyceride Glycidyl ester, di-glycidyl ortho-phthalate Be ether, hydroquinone diglycidyl ether, bisphenol S diglycidyl ether, terephthalic acid diglycidyl ether, dibromo neopentyl glycol diglycidyl ether, epoxy cresol novolac resin emulsion, also be used as modified bisphenol A type epoxy emulsion.

It is also preferable to use a crosslinking agent having an alkoxysilyl group as a functional group. Since the alkoxysilyl group becomes a reactive silanol group by hydrolysis, it can be easily chemically bonded to an amino group or a carboxylic acid group present in a mucopolysaccharide or silk-derived protein. In addition, since there are a large number of functional groups bonded to the epoxy group, the degree of freedom in selecting as a binder base is increased. For this reason, it is possible to select from among a large number of binder bases that are excellent in water resistance, hardly yellowed, are soft and have a good texture. As the crosslinking agent having an alkoxysilyl group, dialkoxysilyl compounds and trialkoxysilyl compounds can be used in addition to monoalkoxysilyl compounds.
Specific examples of such a crosslinking agent include vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxy. Propylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, γ-metaglyoxypropylmethyldimethoxysilane, γ-metaglyoxypropyltrimethoxysilane,
γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxytrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (amino Ethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-triethoxysilyl-N -(1,3-dimethylbutylidene) propylamine, N-phenyl-γ-aminopropyltrimethoxysilane and the like.

  The cross-linking agent preferably has a hydrophilic group. Since the functional component mucopolysaccharide and silk-derived protein are water-soluble substances, if the crosslinking agent has a hydrophilic group, the reaction between the crosslinking agent and the functional component can be easily performed. As such a cross-linking agent having a hydrophilic group, any substance that forms a cross-linked structure by chemically bonding with the functional group and functional component of the binder base can be used. Among these, a crosslinking agent having an epoxy group bonded to a polyether chain is particularly suitable. This is because with such a crosslinking agent, the hydrophilicity is increased by the polyether chain, so that it can be easily reacted with water-soluble functional components such as mucopolysaccharides and silk-derived proteins. Examples of such a polyether chain include a polyethylene glycol chain and a polypropylene glycol chain. Among them, the polyethylene glycol chain is particularly suitable because of its high hydrophilicity. In this case, the number n of the repeating units of the polyethylene glycol chain is preferably 10 or less. When the polyethylene glycol chain is 10 or less, the reaction activity of the crosslinking agent is increased. The range of 2 to 4 is more preferable. A polyethylene glycol chain within this range is easy to synthesize, inexpensive, highly reactive, and hydrophilic, so that a crosslinking reaction can be easily performed.

  As the binder base, any polymer having a functional group chemically bonded to the functional group of the crosslinking agent can be used. If the binder base is silicone or a mixture of an acrylic polymer emulsion and a silicone emulsion, it can be chemically bonded to the functional group of the crosslinking agent by the terminal hydroxyl group present in the silicone, and the texture is supple and suitable.

  The contact cooling sensation fiber of this invention can be manufactured by processing a fiber with the fiber treatment agent of this invention. That is, the fiber treatment agent of the present invention includes a functional component composed of at least one of mucopolysaccharide and silk-derived protein, and a binder for attaching the functional component to the fiber. An emulsion of a binder base composed of a polymer, and a crosslinking agent having a plurality of functional groups capable of forming a crosslinked structure by chemically bonding with the functional groups and functional components of the binder base. It is characterized by.

  In order to produce the contact cooling sensation fiber of the present invention using the fiber treatment agent of the present invention, first, fibers and fabrics are immersed in the aqueous solution of the fiber treatment agent of the present invention. Then, it becomes the contact cooling sensation fiber of this invention by making it dry. In the drying step, the binder base emulsion made of a polymer forms a binder base coating layer on the fiber surface. The functional group of the binder base and the functional group of the cross-linking agent are bonded to each other, and the amino group or carboxylic acid group of the functional component is chemically bonded to the functional group of the cross-linking agent to cross-link the binder base coating layer. The functional component is modified by a chemical bond through the agent. In this way, the contact cooling sensation fiber can be manufactured very easily.

  Examples in which the present invention is further embodied will be described below in comparison with comparative examples.

（商品名：ＫＴ−７０１４ 高松油脂株式会社製）・・・・・・３質量％
・ポリエチレングリコールジグリシジルエーテル（架橋剤） ０．５質量％
（商品名：ＣＡＴ−ＳＰ−５ 高松油脂（株）製）
ポリエチレングリコール鎖の重合度ｎ＝２、下記構造式参照）

・柔軟剤（ポリアミン樹脂・アミノシリコーン分散物の混合体）・１質量％
（商品名：ラノテックスＹＯ 高松油脂（株）製）
・コンプレックス防止剤
（商品名：スカルナーＤＮ 高松油脂（株）製）・・・・０．５質量％
・水・・・・・・・・・・・・・・・・・・・・・・・・・・・・ 残部 Example 1
In Example 1, a fiber treatment agent having the following composition was prepared.
・ Silk fibroin 5% aqueous solution ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 8% by mass
(Product name: NATURAS SP-5 manufactured by Takamatsu Yushi Co., Ltd.)
-Mucopolysaccharide dispersion ... 10% by mass
(Product name: Finish Agent SK Takamatsu Yushi Co., Ltd.)
・ Silicone emulsion (binder base, see chemical formula below)

(Product name: KT-7014, Takamatsu Yushi Co., Ltd.) ··· 3% by mass
・ Polyethylene glycol diglycidyl ether (crosslinking agent) 0.5% by mass
(Product name: CAT-SP-5, Takamatsu Yushi Co., Ltd.)
Degree of polymerization of polyethylene glycol chain n = 2, see the structural formula below)

・ Softener (mixture of polyamine resin and aminosilicone dispersion) ・ 1% by mass
(Product name: Lanotex YO Takamatsu Yushi Co., Ltd.)
・ Anti-complex agent (trade name: Skulner DN, manufactured by Takamatsu Yushi Co., Ltd.) ... 0.5% by mass
・ Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Balance

(Example 2)
In Example 2, a fiber treating agent having the following composition was prepared.
・ Silk fibroin 5% aqueous solution ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5% by mass
(Product name: NATURAS SP-5 manufactured by Takamatsu Yushi Co., Ltd.)
-Mucopolysaccharide dispersion ... 10% by mass
(Product name: Finish Agent SK Takamatsu Yushi Co., Ltd.)
・ Mixture of polyalkyl acrylate copolymer emulsion and silicone emulsion (binder base)
(Product name: TK binder-SF manufactured by Takamatsu Yushi Co., Ltd.) ... 5% by mass
・ Polyethylene glycol diglycidyl ether (crosslinking agent)
0.5% by mass
(Same as Example 1)
・ Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Balance

(Example 3)
In Example 3, a fiber treatment agent having the following composition was prepared.
・ Silk fibroin 5% aqueous solution ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5% by mass
(Product name: NATURAS SP-5 manufactured by Takamatsu Yushi Co., Ltd.)
Silicone emulsion (same binder base as in Example 1)
(Product name: KT-7014, Takamatsu Yushi Co., Ltd.) 3 mass%
・ Polyethylene glycol diglycidyl ether (crosslinking agent) ・ 0.5% by mass
(Same as Example 1)
・ Anti-complex agent (trade name: Skulner DN, manufactured by Takamatsu Yushi Co., Ltd.) ... 0.5% by mass
・ Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Balance

Example 4
In Example 4, a fiber treating agent having the following composition was prepared.
-Mucopolysaccharide dispersion: 10% by mass
(Product name: Finish Agent SK Takamatsu Yushi Co., Ltd.)
Silicone emulsion (same binder base as in Example 1)
(Product name: KT-7014, Takamatsu Yushi Co., Ltd.) 3 mass%
・ Polyethylene glycol diglycidyl ether (crosslinking agent) ・ 0.5% by mass
(Same as Example 1)
・ Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Balance

(Example 5)
In Example 5, a fiber treating agent having the following composition was prepared.
・ Silk fibroin 5% aqueous solution ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5% by mass
(Product name: NATURAS SP-5 manufactured by Takamatsu Yushi Co., Ltd.)
-Mucopolysaccharide dispersion: 10% by mass
(Product name: Finish Agent SK Takamatsu Yushi Co., Ltd.)
Silicone emulsion (same binder base as in Example 1)
(Product name: KT-7014, Takamatsu Yushi Co., Ltd.) 3 mass%
・ Polyethylene glycol diglycidyl ether (crosslinking agent) ・ 0.5% by mass
(Same as Example 1)
・ Anti-complex agent (trade name: Skulner DN, manufactured by Takamatsu Yushi Co., Ltd.) ... 0.5% by mass
・ Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Balance

・コンプレックス防止剤
（商品名：スカルナーＤＮ 高松油脂（株）製）・・・・０．５質量％
・水・・・・・・・・・・・・・・・・・・・・・・・・・・・・・残部 (Example 6)
In Example 6, a fiber treating agent having the following composition was prepared.
・ Silk fibroin 5% aqueous solution ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 8% by mass
(Product name: NATURAS SP-5 manufactured by Takamatsu Yushi Co., Ltd.)
-Mucopolysaccharide dispersion: 10% by mass
(Product name: Finish Agent SK Takamatsu Yushi Co., Ltd.)
Silicone emulsion (same binder base as in Example 1)
(Product name: KT-7014, Takamatsu Yushi Co., Ltd.) 3 mass%
・ Γ-Glycidoxypropyltrimethoxysilane (crosslinking agent) ・ 0.5% by mass
(See the chemical formula below)

・ Anti-complex agent (trade name: Skulner DN, manufactured by Takamatsu Yushi Co., Ltd.) ... 0.5% by mass
・ Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Balance

  The fiber treatment agent of Examples 1 to 6 is put in a pad, and the polyester woven fabric (material: polyethylene terephthalate) is passed through the pad to immerse the polyester woven fabric in the fiber treatment agent, followed by squeezing treatment. (Pick up rate 80%). And the contact cooling feeling fiber fabric of Example 1- Example 6 was obtained by performing drying for 3 minutes at 110 degreeC, and also heat-processing for 1 minute at 160 degreeC.

(Comparative Example 1)
The contact cooling sensation fiber of Comparative Example 1 is a commercially available contact cooling sensation fiber fabric in which ethylene vinyl alcohol fiber is blended with polyester fiber.

(Comparative Example 2)
The contact cooling sensation fiber of Comparative Example 2 is a commercially available contact cooling sensation fiber fabric using rayon fibers kneaded with polymer microcapsules that cause a phase change at body temperature and take away latent heat.

(Comparative Example 3)
The contact cooling sensation fiber of Comparative Example 3 is a commercially available contact cooling sensation fiber fabric in which special inorganic particles having high thermal conductivity are kneaded in a nylon polymer.

  For the contact-cooled fiber fabrics of Examples 1 to 6 and Comparative Examples 1 to 3, measurement of q-max (numerical value representing coldness and warmth felt when a person touches the fabric) and contact by the following method A cool feeling test, a texture test, a discoloration test, and a friction fastness test were performed.

The q-max measurement method q-max was measured using a precise rapid thermophysical property measuring apparatus (trade name: Thermolab II type, manufactured by Kato Tech Co., Ltd.). As shown in FIG. 1, this apparatus includes a sample stage 2 on which a fabric 1 serving as a sample is attached, and a detector 3. A copper thin plate 3 a is attached to one surface of the detector 3, and a temperature sensor 3 b is attached to the back surface of the copper thin plate 3. A heater (not shown) is attached to the sample stage 2 and the detector 3, and the temperature can be set independently by a control device (not shown).

First, as shown in FIG. 1A, the sample stage 2 and the detector 3 are separated from each other, and the cloth 1 to be measured is attached to the sample stage 2. And the sample stand 2 was set to 20 degreeC with the control apparatus, and the temperature of the copper thin plate 3a of the detector 3 was set to 30 degreeC. Thereafter, as shown in FIG. 1B, the sample output 2 is brought into contact with the copper thin plate 3a of the detector 3, and at the same time, the sensor output from the temperature sensor 3b is recorded. At this time, the copper thin plate 3a is deprived of heat by the sample stage 2 through the fabric 1, and the temperature is lowered. When the temperature change curve thus obtained is differentiated by time, the maximum value appears immediately after the copper thin plate 3a is brought into contact with the sample stage 2. The maximum heat adsorption rate at this time was defined as q-max. It has been found that the q-max value and the sensory test result of the contact cooling sensation performance by an expert show a good correlation. Moreover, the greater the value of q-max, the greater the feeling of cooling when touched by a person. Specifically, if q-max is 0.1 or more, a person can feel contact cold sensation.
In addition, each sample measured about what did not wash, what repeated washing 10 times, and what repeated washing 20 times.

Contact cooling sensation test In the contact cooling sensation test, the test piece was left in an atmosphere of 60% RH at 20 ° C. for 5 hours, and then contacted with the back and arms of the subject's hand for 1 minute. 6 levels from 1 to 6 ("1" is not felt, "2" is negligible, "3" is slightly felt, "4" is felt, "5" is quite felt, "6""I feel strongly").

Texture test The texture test is a six-stage feel of the subject touching the test piece (1 to 6), "2" is a bit irritating, "3" is a little irritating, "3" is normal, "4" is a little ("5" feels soft, "6" feels very soft).

Discoloration test In the discoloration test, the color change before and after the setting step in preparing a contact-cooled fiber fabric was visually determined.

Friction fastness test The friction fastness test was performed according to the method of JIS L0849-II.

(Result)
The results of the above tests are shown in Tables 1 to 5.

  From Table 1, it can be seen that the contact cooling sensation fibers of Examples 1 to 6 are superior to the contact cooling sensation fibers of Comparative Example 1 and Comparative Example 2 in contact cooling sensation performance. In addition, the firmness to washing is excellent. This is because the mixture of silk fibroin and mucopolysaccharide, which are functional components for exerting a cool feeling of contact, and a silicone emulsion or polyalkyl acrylate copolymer emulsion as a binder base and a silicone emulsion is a polyethylene glycol as a crosslinking agent. This is because a cross-linked structure is formed by chemically bonding with the epoxy group of diglycidyl ether. Particularly in Example 1 and Example 2 containing both silk fibroin and mucopolysaccharide, the contact cooling feeling performance was particularly excellent due to the synergistic effect of the functional components. Moreover, as shown in Table 2, also in the contact cooling sensation sensory test, Example 1 and Example 6 had the outstanding contact cooling sensation performance.

  Further, the contact cooling sensation fibers of Comparative Examples 1 to 3 must be made into a woven fabric after producing special fibers having a cooling sensation effect in advance. On the other hand, in the contact cooling sensation fibers of Examples 1 to 6, it is possible to impart a cooling effect by post-processing. For this reason, manufacture was easy and the manufacturing cost was low.

  Moreover, as shown in Table 3, Examples 1 to 6 were soft and had a good texture, and among them, Examples 1 and 6 to which a softening agent was added were particularly good.

Furthermore, as shown in Table 4, in the color change test, Examples 1 to 6 did not show any visible color change before and after setting. This is because a silane-based or epoxy-based cross-linking agent that hardly changes color is used. From the above results, it was found that silane-based and epoxy-based crosslinking agents are preferable as the crosslinking agent used in the fiber treatment agent of the present invention.

  Moreover, as shown in Table 5, the friction fastness of Examples 1-6 was 3.5-4.0, and it turned out that it has high friction fastness.

It is a schematic diagram of a precise rapid thermophysical property measuring apparatus.

Explanation of symbols

1. Fabric (contact cooling fiber)
2 ... Sample stand 3 ... Detector 3a ... Copper sheet 3b ... Temperature sensor

Claims (15)

A functional component consisting of at least one of mucopolysaccharide and silk-derived protein is fixed to the fiber surface by a binder,
The binder includes a binder base made of a polymer, a functional group of the binder base, and a cross-linking agent having a plurality of functional groups capable of forming a cross-linked structure by chemically bonding with the functional component. A contact-cooled sensation fiber characterized by comprising   The contact cooling sensation fiber according to claim 1, wherein the crosslinking agent has at least one of an epoxy group and an alkoxysilyl group as a functional group.   The contact cooling sensation fiber according to claim 1, wherein the crosslinking agent has a hydrophilic group.   The contact cooling sensation fiber according to claim 3, wherein the crosslinking agent is a compound in which an epoxy group is modified on a polyether chain as a hydrophilic group.   The contact cooling sensation fiber according to claim 4, wherein the polyether chain is a polyethylene glycol chain.   The contact cooling sensation fiber according to claim 5, wherein the number n of repeating units of the polyethylene glycol chain is 1 to 10.   The contact cooling sensation fiber according to any one of claims 1 to 6, wherein the binder base is silicone.   The contact cooling sensation fiber according to any one of claims 1 to 7, wherein the binder base is a mixture of an acrylic polymer emulsion and a silicone emulsion.   The contact cooling sensation fiber according to any one of claims 1 to 8, wherein the functional component contains at least one of silk fibroin and sericin.   A functional component composed of at least one of mucopolysaccharide and silk-derived protein and a binder for adhering the functional component to fibers are contained, and the binder is an emulsion of a binder base composed of a polymer. And a crosslinking agent having a plurality of functional groups capable of forming a crosslinked structure by chemically bonding with the functional groups and functional components of the binder base. .   11. The fiber treatment agent according to claim 10, wherein the crosslinking agent is a compound in which an epoxy group is modified on a polyether chain.   The fiber treatment agent according to claim 11, wherein the polyether chain is a polyethylene glycol chain.   The fiber treatment agent according to claim 12, wherein the number n of repeating units of the polyethylene glycol chain is 1 to 10.   The fiber treatment agent according to any one of claims 10 to 13, wherein the binder base is silicone.   The fiber treatment agent according to any one of claims 10 to 13, wherein the binder base is a mixture of an acrylic polymer emulsion and a silicone emulsion.

Images