WO2004005607A1 - Fiber processing agent and fiber processed with the fiber processing agent - Google Patents

Abstract

A fiber processing agent to be used in processing fiber surface which contains a soluble eggshell membrane and a reactive organic compound having a reactive group. When processed with the fiber processing agent having the above constitution, a fiber can sustain the characteristics of the eggshell membrane even after being used over a long time without losing the eggshell membrane components. Thus, it can continuously achieve a good tolerance and favorable moisture retention, water-absorbing property, moisture-absorbing property, antistatic property and wound-treating property.

Description

Fiber treatment agent and fibers treated with this fiber treatment agent

Technical field

 The present invention relates to a fiber treatment agent and fibers treated with the fiber treatment agent.

Background art

 Conventionally, blouse, dress shirts, pants, skirts, lining, furniture, vehicles, etc.

Products using fibers such as skin materials for seats are on the market.

 These textiles differ in the properties required for the fiber used as the material due to differences in various uses. These required properties include, for example, moisture retention, water absorption, moisture absorption, antistatic properties, and the like.

 For example, in the case of a blouse, they often wear sweat because they are worn everyday. Therefore, it is required to have a hygroscopic property. In order to satisfy this hygroscopicity, various fibers are used. Examples of the fiber include synthetic fibers such as nylon, polyester, acrylic, and polyurethane, and natural fibers such as cotton, hemp, and wool, and also include composite fibers thereof.

 On the other hand, by treating these fibers with a specific fiber treating agent, attempts have been made to improve the above-mentioned properties or to provide special properties in addition to the above-mentioned properties.

 For example, in addition to improving the above properties, eggshell membranes have the effect of accelerating the healing of the wound when applied to the wound surface of the skin, so-called wound healing properties, making it easy to apply to large wound surfaces. It is known that eggshell membrane powder is mixed with a fiber material and then thinly formed into a sheet material for use in treating wounds.

By the way, in the above-mentioned sheet material made of a fiber material having a wound healing property, in order to make the wound healing property more effective, an eggshell membrane is prepared as a soluble aqueous solution. Soak a sheet of nonwoven fabric and dry it to make the sheet material A production method has been proposed (see Japanese Patent Application Laid-Open No. 7-24632).

 This method does not cause any problem in the case of one-time use such as disposable, because it naturally exhibits properties such as wound healing properties.

 However, in the technology described in the above-mentioned publication, a sheet such as a woven fabric or a nonwoven fabric is immersed in an aqueous solution containing only an eggshell membrane and dried, so that the eggshell membrane has low adhesion to the sheet material. Therefore, for example, when the sheet material is repeatedly washed or used for a long period of time, the eggshell membrane is removed, the durability is reduced, and the moisture retention, water absorption, moisture absorption, There is a problem that characteristics such as electrical conductivity and wound healing cannot be maintained. Disclosure of the invention

 An object of the present invention is to provide a fiber treating agent having good durability, capable of continuously exhibiting moisturizing properties, water absorbing properties, moisture absorbing properties, antistatic properties, and wound healing properties. To provide treated fibers. The fiber treating agent of the present invention is a fiber treating agent used when treating a fiber surface, and comprises a soluble eggshell membrane and a reactive organic compound having a reactive group.

 In the present invention, the term "soluble eggshell membrane" refers to an eggshell membrane obtained by transforming the eggshell membrane of a bird egg (typically a chicken egg) into a water-soluble form by treating it with a chemical such as an acid, an alcohol, an oxidizing agent, or a reducing agent. Say.

 As a bird egg used for the eggshell membrane, chicken eggs and bird eggs such as duck, quail and ostrich can be used.

 Representative examples of the reducing agent used in the chemical treatment include thioglycolic acid, thiopropionic acid, 2-mercaptoethanol, and the like.

In preparing the soluble eggshell membrane used for producing the fiber treatment agent, first, an aqueous solution of the soluble eggshell membrane may be prepared and prepared by an arbitrary method. Some typical preparation methods are described below. One part by weight of eggshell membrane is mixed with thioglycolic acid (14. 3 mo 1) Add 10 to 32 parts by weight of dithiopropionic acid (11.3 mo 1), or a mixture of these, with a concentration of lmo 1 liter or more in aqueous solution. This is heated to about 50 to 70 ° C and kept for 5 to several tens of hours until the eggshell membrane is completely dissolved. Next, the used reducing agent is removed to obtain an aqueous solution.

 Specifically, acetone is added to the above-mentioned treatment solution to precipitate a soluble and dissolved eggshell membrane, then the solution (reducing agent) is removed, and then the precipitate is washed once or twice with acetone. Then, add water to make an aqueous solution.

 As another method, the reducing agent solution in which the eggshell membrane is dissolved is acidified with hydrochloric acid to prevent oxidation, and then the reducing agent is removed by dialysis against water.

 When 2-mercaptoethanol is used as a reducing agent, the treatment is carried out at 50 to 70 ° C for 5 to several tens of hours with an alkaline side of pH 9 to 10 to enhance the reducing power. In this case, it is difficult to completely dissolve the eggshell membrane, so the treatment was stopped for a certain period of time, centrifuged to remove insolubles, and then dialyzed with water or precipitated by dissolving the eggshell membrane with acetone and collected. Then, an aqueous solution of a soluble eggshell membrane is prepared by, for example, dissolving in water.

 In addition, when preparing a soluble eggshell membrane by alkali decomposition, an aqueous solution or an aqueous solution containing 1 to several N (normal) of sodium hydroxide per 1 part by weight of the eggshell membrane is used.

(Alcohol concentration of 50 to 70%, etc.), and treat at 40 to 60 ° C for 3 to 6 hours. In the fiber treating agent of the present invention, the reactive organic compound is (Component 1) a hydrophilic compound having a polymerizable vinyl group in a molecule, (Component 2) a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, or a phosphorus compound. It is preferable to include at least one of a monomer containing an acid group, (Component 3) a hydrophilic compound having an epoxy group, and (Component 4) a compound having an aziridine group.

Specific examples of the aforementioned (Component 1) include polyethylene glycol diatalylate, polyethylene glycol dimethacrylate, bisphenol A / polyethylene glycol dimethacrylate, bisphenol A polyethylene glycol dimethacrylate, and bisphenol S polyethylene dalicol diethylene glycol. Such as methacrylate. Specific examples of the above (Component 2) include acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamide, methacrylamide, vinylsulfonic acid, and hydroxypropyl methacrylate.

 Specific examples of the above (Component 3) include polyethylene glycol diglycidyl ether and the like.

 A specific example of the above (Component 4) is a compound represented by the following chemical formula (1).

CH ₃

 I

CH2 = C

I / CH ₂ —— (1)

COOCH2CH2N ί I

 CH2

 In the present invention, the aqueous solution of the soluble eggshell membrane described above and a reactive organic compound are prepared to prepare a fiber treating agent.

 In addition to the soluble eggshell membrane and the reactive organic compound, fibrous mouth, sericin, chitosan and the like may be blended. By blending these, the effect of improving the hygroscopicity can be obtained. According to the present invention, by containing a reactive organic compound having a reactive group, the eggshell membrane is not removed even when the fiber-treated fiber is used for a long time. Therefore, since the characteristics of the eggshell membrane can be maintained, the fiber treatment agent has good durability, and can continuously exhibit moisture retention, water absorption, moisture absorption, antistatic properties, and wound healing properties. Can be.

In the fiber treatment agent of the present invention, the soluble eggshell membrane is contained in an amount of 0.1 to 10% by mass, and the reactive organic compound is contained in an amount of 1 to 20% by mass, based on the total amount of the fiber treatment agent. Is preferred. More preferably, the soluble eggshell membrane is contained at 0.2 to 5% by mass, and the reactive organic compound is contained at 2 to 10% by mass. When the amount of the soluble eggshell membrane is less than 0.1% by mass and the amount of the reactive organic compound is less than 1% by mass, effects such as moisture retention become insufficient. Further, when the soluble eggshell membrane exceeds 10% by mass and the reactive organic compound exceeds 20% by mass, the fiber to be treated may be hardened. The fiber treating agent of the present invention may have the following configuration.

 The fiber treating agent of the present invention is a fiber treating agent used when treating the surface of a fiber, and is characterized by containing a soluble eggshell membrane and an organic compound having a fixing property.

 Here, the soluble eggshell membrane is as described above as the soluble eggshell membrane contained in the fiber treatment agent of the present invention, and thus the description is omitted here. In the fiber treatment agent of the present invention, a reactive organic compound having a reactive group can be used as the organic compound having the fixing property.

 According to the present invention, it is possible to prevent the eggshell membrane from being removed even when the fiber-treated fiber is used for a long period of time.

 In the fiber treating agent of the present invention, the reactive organic compound includes (Component 1) a hydrophilic compound having a polymerizable vinyl group in a molecule, (Component 2) a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, A monomer containing a phosphate group, (component 3) a hydrophilic compound having an epoxy group, (component 4) a compound having an aziridine group, (component 5) a compound having an isocyanate group or a precursor thereof. It preferably contains at least one of components 1) to (component 5).

 Specific examples of (Component 1) to (Component 4) contained in the reactive organic compound are the same as (Component 1) to (Component 4) described above as the fiber treatment agent of the present invention. Here, the description is omitted.

 Among (Component 5), specific examples of the compound having an isocyanate group include hexamethylene diisocyanate represented by chemical formulas (i) and (ii) and 1,3,5-triisocyanate n-pentane Etc. can be mentioned.

OCN- (CH2) 6-NCO (i)

_{OC - (CH 2) 2-} CH - (CH 2) 2 -NCO (ϋ)

 NCO

Among the (Component 5), as a specific example of the compound having a precursor of an isocyanate group, Examples thereof include a precursor of hexamethylene diisocyanate and a precursor of 1,3,5-triisocyanate-1-η-pentane. Among them, the precursors of hexamethylene diisocyanate include 1,6-di (methylcarbamoyl) -1n-hexane and 1,6-di (phenylcarbamoyl) shown in chemical formulas (iii) and (iv). 1) n-hexane. Further, as a precursor of 1,3,5-triisocyanate-n-pentane, a compound represented by a chemical formula (V) can be given.

 H 0

 I II

 C-1 0-C-1 N-(C) 6-N-C-1 0— CH3 (ill.

 0 H

 H H

<o O- C -N- (CH2) 2-CH-(CH ₂ ) 2-N -C-0- <o) ( _v )

 II I Π

O H-N O

 C = 0

 O In the fiber treating agent of the present invention, a lipophilic compound such as wax or silicone and a polymer compound containing a group such as z or ether, acryl, urethane, amide, or ester are used as the organic compound having the sticking property. can do.

 Non-reactive as an organic compound having stickiness, it is an organic compound that itself has moderate lipophilicity or hydrophilicity and sticks to the fiber surface, and is used as a softener for fibers and fabrics, and as a smooth finish. Organic compounds used for agents, antistatic agents and the like. Specific examples of the lipophilic compound include waxes and silicones, as well as neutral fats and oils, mineral oils, animal animals, and the like. Examples of the polymer compound include polyethylene glycol (di) Alkylates, polyhydric alcohol esters, polyalkylamides, polyatalylates and the like can be mentioned.

According to the present invention, such a lipophilic compound and / or polymerized The compound adheres to the fiber surface and can prevent the eggshell membrane protein immersed in the fiber from eluting out of the fiber. Therefore, similarly to the reactive organic compound, it is possible to prevent the eggshell membrane from being removed even when the fiber-treated fiber is used for a long time. The fiber of the present invention is characterized in that it has been treated with the fiber treating agent of the present invention described above.

 Examples of the fiber to be treated include synthetic fibers such as nylon, polyester, acrylic, and polyurethane, and natural fibers such as cotton, hemp, and wool, and composite fibers thereof.

 As a treatment method of the fiber treatment agent, any treatment method may be used. For example, a dipping method, a padding method, or the like can be used. Examples of the immersion method include a room temperature standing method and a heating and stirring method. The padding method includes a pad dry method and a pad steam method. Of these, any method may be used in the case of a reactive organic compound. In the case of a non-reactive compound, it is preferable to use a pad dry method.

 According to the present invention, by being treated with the above-mentioned fiber treating agent, it has excellent durability, and continuously exhibits moisture retention, water absorption, moisture absorption, antistatic properties, and wound healing properties. The resulting fiber can be. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

 [Example 1]

 In preparing the fiber treatment agent, first, an aqueous solution of a soluble eggshell membrane was prepared. After the eggs with shells are broken to remove the egg solution, the resulting eggshells with eggshell membranes are placed in clean water, the eggshells are removed by hand, and the eggshell membranes are immersed in a 1% aqueous hydrochloric acid solution for 1 hour. After immersion, the fine eggshell attached to the eggshell membrane was dissolved, washed with water and air-dried to obtain an eggshell membrane.

To 50 g of the eggshell membrane, 1.5 liters of an aqueous solution of 5.0 mo 1 Z liters of thiodalicholate was added. An aqueous solution of tidalicholic acid containing eggshell membranes at 60 ° C for 12 hours Heat treatment dissolves the eggshell membrane.

 After filtering the aqueous solution in which the eggshell membranes were dissolved, the solution was dialyzed against hydrochloric acid water to remove thioglycolic acid, thereby obtaining a soluble eggshell membrane aqueous solution.

 Next, the aqueous solution of the soluble eggshell membrane obtained above and a reactive organic compound were blended to prepare a fiber treating agent. The concentration of each component of the fiber treatment agent is as follows. 5.0% by mass of solid content of soluble eggshell membrane

 89.5 mass% water

 Reactive organic compound (compound of the following chemical formula (2)) 5.0% by mass

 Reactive organic compound (compound of the following chemical formula (3)) 0.5% by mass

CH2 = C— C— 0— (C ₂ H4〇) 23— C— C = C

 (2)

 O O CH3

CH ₃

CH3 CH3

 I I

HC1 -HN = C— C— N = N— C-C = NH-HC1 (3)

 NH2 CH3 NH2 CH3

 Using the resulting fiber treatment agent, 100% polyester taffeta fabric

(Basis weight: 120 gm ² ), and after reducing the impregnation rate to 70% with a mandal, perform steam heat treatment at 105 ° C for 10 minutes, and then wash with hot water (40 ° C, 0 minutes) ), Drying and heat setting.

 [Example 2]

 The taffeta woven fabric obtained in the same manner as in Example 1 was washed with a fully automatic household washing machine, washed for 15 minutes, rinsed twice, and washed 10 times.

 [Example 3]

 A fiber treating agent according to the second invention of the present invention was prepared by blending a soluble eggshell membrane aqueous solution and light silicone PS-1000 (manufactured by Kyoeisha Chemical Co., Ltd.), which is an organic compound having adhesive properties. The aqueous solution of a soluble eggshell membrane used for the preparation of this fiber treatment agent was prepared by the preparation method described in Example 1.

Soluble eggshell membrane solids 10.0 mass ° / ₀ W Write silicone PS- 1 000 1 0. 0 mass ^_0/0

 Water 80.0% by mass

Next, the obtained fiber treating agent was impregnated into a 100% polyester taffeta woven fabric (having a basis weight of 120 g / m ² ) and then squeezed to 70% with a mandal. Thereafter, the obtained tufted fabric is dried in a hot air drier at 150 ° C. for 5 minutes, and rinsed in the same manner as in Example 2, that is, for 15 minutes with a home automatic washing machine. Washing was performed 10 times, with washing being one time.

 [Comparative Example 1]

 The same 100% polyester taffeta fabric as in Example 1 was used, but no treatment with a fiber treating agent or the like was performed.

 [Comparative Example 2]

 Example 2 is different from Example 1 in that the fiber treatment agent contains only a soluble eggshell membrane. The concentration of each component of the fiber treatment agent is as follows.

 Soluble eggshell membrane solids' 5% by mass

 Water 95% by mass

 Thereafter, washing was performed 10 times in the same manner as in Example 2.

 [Comparative Example 3]

 A taffeta fabric was prepared in the same manner as in Example 3 described above, using a fiber treating agent prepared with the following composition.

 Solid content of soluble eggshell membrane 10.0% by mass

 Water 90.0% by mass

 Next, the obtained taffeta fabric was washed 10 times in the same manner as in Example 3.

 [Reference Example 1]

 A taffeta woven fabric was prepared in the same manner as in Comparative Example 3 described above, using a fiber treating agent prepared with the following composition.

Light Silicone PS- 1 000 10. 0 mass ^_0/0

 Water 90.0% by mass

Next, the obtained taffeta fabric was washed 10 times in the same manner as in Example 3. [Evaluation method 1]

 With respect to the taffeta fabric according to the first invention of Examples 1 and 2 and Comparative Examples 1 and 2, the hygroscopicity, the water absorption speed, and the frictional voltage were measured. Further, with respect to the taffeta fabric according to the second invention of Example 3, Comparative Example 3, and Reference Example 1, the water absorption rate and the friction voltage were measured. The moisture absorption was measured by leaving a sample of the stuffed fabric at 23 ° C and a relative humidity of 30% for 12 hours to adjust the humidity. The measurement was performed by placing the sample in a 0% atmosphere and measuring the change in weight. The water absorption was measured in accordance with the JIS L106-A method. The friction band voltage is J I S L

1 0 9 4—Measured in accordance with Method B. Table 1 shows the evaluation results.

 (table 1 )

この評価方法 1の評価結果によれば、 実施例 1の方が、 比較例 1よりも、 吸湿 性、吸水速度が高く、摩擦帯電圧が小さく、全ての点で優れていることがわかる。 従って、 本発明にかかる繊維処理剤 （反応性有機化合物を含有するもの） により 処理を行った繊維は、 吸水性、 吸湿性、 制電性について向上することがわかる。 また、 実施例 2と比較例 2を比較すると、 吸湿性、 吸水速度が高く、 摩擦帯電 圧が小さく、 全ての点で優れていることがわかる。 従って、 本発明にかかる繊維 処理剤 （反応性有機化合物を含有するもの） により処理を行った繊維は、 洗濯を しても、 効果が持続しているので、 耐久性に優れていることがわかる。

According to the evaluation results of this evaluation method 1, it is found that Example 1 has higher hygroscopicity and water absorption speed, a lower frictional voltage, and is superior in all respects to Comparative Example 1. Therefore, it is understood that the fiber treated with the fiber treating agent (containing a reactive organic compound) according to the present invention has improved water absorption, moisture absorption, and antistatic properties. In addition, comparing Example 2 with Comparative Example 2, it can be seen that it has excellent hygroscopicity, high water absorption rate, low triboelectric charging pressure, and all points. Therefore, it can be seen that the fiber treated with the fiber treating agent (containing a reactive organic compound) according to the present invention has excellent durability even after washing, since the effect is maintained. .

In Comparative Example 2, in the initial state without washing, the moisture absorption 、 was 2. The water absorption rate was 0%, the water absorption rate was 1 second or less, and the friction band voltage was 500 V. From a comparison between the initial state and the state after washing, it can be seen that there is no durability when the fiber treatment agent contains only the soluble eggshell membrane as in the past.

 Further, when Example 3 is compared with Comparative Example 3, it can be seen that Example 3 has higher water absorption rate, lower frictional band voltage, and is superior in all respects to Comparative Example 3. The same can be said when Example 3 is compared with Reference Example 1. Therefore, it can be seen that the fibers treated with the fiber treating agent of the present invention (containing an organic compound having a sticking property) have improved water absorption and antistatic properties.

 [Evaluation method 2]

 After affixing a commercially available adhesive tape to the skin and peeling it off, creating a rough skin with acetone-Z ether solution, using the taffeta fabric cloth created in Examples and Comparative Examples on the upper arm, for 6 hours daily, for a specified number of days, The conductance of the upper arm that was fixed and wound with this cloth was measured. Table 2 shows the evaluation results.

 (Table 2)

この評価方法 2の評価結果によれば、 実施例 1の方が、 比較例 1よりも、 コン ダクタンスが大きくなっていることがわかる。 このコンダクタンスの値が大きレ、 程、 肌の伝導度があがり、 肌荒れした部分の肌が再生していることと、 肌の保湿 状態が高まっていることを示している。

According to the evaluation result of this evaluation method 2, it is understood that the conductance of Example 1 is larger than that of Comparative Example 1. The higher this conductance value is, the higher the conductivity of the skin is, indicating that the skin in the roughened part is being regenerated and the moisturizing condition of the skin is increasing.

Therefore, the fiber treated with the fiber treating agent (containing a reactive organic compound) according to the present invention has improved wound healing properties and moisturizing properties because the roughened skin is regenerated. You can see that it is doing. Furthermore, even when used for a long period of time as in the test of this evaluation method 2, the effects of wound healing and moisturizing properties are recognized, indicating that each property can be maintained for a long period of time. . Industrial applicability

 INDUSTRIAL APPLICABILITY The present invention can be used as a fiber treatment agent for improving the properties of fibers such as moisture retention, water absorption, moisture absorption, and antistatic properties, or as a fiber or fiber product having these properties improved.

Claims

The scope of the claims 1. A fiber treating agent used for treating a fiber surface,  A fiber treatment agent comprising a soluble eggshell membrane and a reactive organic compound having a reactive group.  2. The fiber treating agent according to claim 1,  The reactive organic compound includes (Component 1) a hydrophilic compound having a polymerizable bullet group in the molecule, and (Component 2) a monomer containing a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and a phosphoric acid group. A fiber treating agent comprising at least one of (Component 3) a hydrophilic compound having an epoxy group, and (Component 4) a compound having an aziridine group.  3. In the fiber treating agent according to claim 1 or claim 2,  The soluble eggshell membrane is contained in an amount of 0.1 to 10% by mass with respect to the total amount of the fiber treating agent,  The fiber treating agent, wherein the reactive organic compound is contained in an amount of 1 to 20% by mass.  4. A fiber which has been treated with the fiber treating agent according to any one of claims 1 to 3.  5. A fiber treating agent used for treating the surface of the fiber,  A fiber treatment agent comprising: a soluble eggshell membrane; and an organic compound having an adhesive property.  6. The fiber treating agent according to claim 5,  The fiber treating agent, wherein the organic compound having a sticking property is a reactive organic compound having a reactive group. 7. The fiber treating agent according to claim 6, The reactive organic compound includes (Component 1) a hydrophilic compound having a polymerizable vinyl group in the molecule, (Component 2) a monomer containing a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and a phosphoric acid group. (Component 3) a hydrophilic compound having an epoxy group, (Component 4) A fiber treating agent comprising at least one of (Component 1) to (Component 5) of a compound having an aziridine group, and (Component 5) a compound having an isocyanate group or a precursor thereof.  8. The fiber treating agent according to claim 5,  The fiber treating agent, wherein the organic compound having the sticking property is a lipophilic compound such as wax and silicone and / or a high molecular compound containing a group such as ether, acryl, urethane, amide, and ester.  9. A fiber which has been treated with the fiber treating agent according to any one of claims 5 to 8.