JP2009228181A - Fiber structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber structure not only allowing once attached stain to be easily removed by washing, but also having excellent stain resistance simultaneously having antistatic properties. <P>SOLUTION: The fiber structure preferably has a resin film obtained by polymerization, on fibers, of a polymerized material composed of a polymerizable monomer having two or more acrylic groups and/or methacrylic groups at both terminals or one terminal of the main chain consisting essentially of a polyalkylene oxide segment, or as a side chain of the main chain, and a cellulose derivative, on the surface of the fibers. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a fiber structure having excellent antifouling properties that can easily remove dirt once adhered by washing and also has antistatic properties.

  Conventionally, many fiber structures having antifouling properties have been proposed. Specifically, a hydrophilic resin having a hydrophilic group such as polyethylene glycol is added to the fiber structure as a means for imparting hydrophilicity to the fiber structure including clothing and the like to remove dirt due to washing (see Patent Document 1). ), Those obtained by polymerizing a hydrophilic vinyl monomer on a fiber (see Patent Document 2), and those using a cellulose derivative, a cellulose graft polymer grafted with an acrylic monomer is obtained by using a melamine-based crosslinking agent or an isocyanate-based polymer. A method has been proposed in which a cross-linking agent, a phenol-based cross-linking agent, a polyvalent metal, or the like is used together and insolubilized to be fixed to a fiber (see Patent Document 3).

  However, the antistatic property can be obtained only by fixing the hydrophilic resin or the polymer of the vinyl monomer, but there is a limit to the washing property for removing dirt.

In addition, those with cellulose derivatives fixed do not have sufficient washing durability, and even when the residual vinyl monomer is grafted and then fixed to the fiber, the resin is easily fixed in a block shape and the stains are fine. In the present situation, it is easy to get into the uneven part, and the removability for washing is not sufficient, and a function such as antistatic property cannot be given.
Japanese Patent Publication No. 48-27066 Japanese Examined Patent Publication No. 6-280164 JP 2004-100111 A

  An object of the present invention is to provide a fiber structure having excellent antifouling properties, which can easily remove dirt once adhered by washing and at the same time has antistatic properties, in view of the background of the above prior art. To do.

  The present invention employs the following means in order to solve the above problems. That is, the fiber structure of the present invention is a polymerizable unit having two or more acrylic groups and / or methacrylic groups as both ends or one end of the main chain mainly composed of a polyalkylene oxide segment or a side chain of the main chain. It is a fiber structure having a resin film formed on a fiber by polymerizing a monomer and a cellulose derivative on a fiber surface.

  According to a preferred aspect of the fiber structure of the present invention, the cellulose derivative is a fiber structure obtained by methoxylation, hydroxyethoxylation or hydroxypropoxylation of a part of the cellulose hydroxyl group.

  According to a preferred aspect of the fiber structure of the present invention, the fiber structure is characterized in that the weight ratio of the polymerizable monomer to the cellulose derivative is in a ratio of 1: 2 to 5: 1.

  According to a preferred aspect of the fiber structure of the present invention, the fiber structure is characterized in that the film is fixed to the fiber surface in a layered manner through a film made of a triazine ring-containing compound.

  According to the present invention, it is possible to obtain a fiber structure that can easily remove dirt once adhered by washing and also has antistatic properties, each having excellent washing durability.

  As a result of intensive studies on the above-mentioned problems, that is, an antifouling fiber structure having excellent washing removability and an antistatic fiber structure having washing durability, the present invention is mainly composed mainly of polyalkylene oxide segments. Polymerized on a fiber using a polymerizable monomer having two or more acrylic groups and / or methacrylic groups as both ends of one chain or one terminal or side chain of the main chain and a cellulose derivative as a polymerization component The present inventors have sought to solve such a problem all at once by forming a resin film.

Examples of the fiber material used in the fiber structure of the present invention include aromatic polyester fibers such as polyethylene terephthalate, polypropylene phthalate and polybutylene terephthalate, aromatic polyester fibers obtained by copolymerizing aromatic polyester with a third component, L -Aliphatic polyester fibers represented by lactic acid as the main component, polyamide fibers such as nylon 6 and nylon 66, acrylic fibers based on polyacrylonitrile, polyolefin fibers such as polyethylene and polypropylene, poly Examples include synthetic fibers such as vinyl chloride fibers, semi-synthetic fibers such as acetate and rayon, and natural fibers such as cotton, silk, and wool. Among these, polyester fiber, polyester fiber / cotton, polyamide fiber, and polyamide fiber / cotton are preferable, and polyester fiber is particularly preferable from the viewpoint of uniformly forming such a polymerized resin. In the present invention, these fibers can be used alone or as a mixture of two or more.

The fiber structure of the present invention includes knitted fabrics using the above-mentioned fibers, fabrics such as woven fabrics and nonwoven fabrics, or string-like products, and clothing using them. Examples of the polymerizable monomer having two or more acrylic groups and / or methacrylic groups as both ends or one end of the main chain or a side chain of the main chain mainly composed of the polyalkylene oxide segment in the present invention include polyethylene. Glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol-polypropylene glycol dimethacrylate, polyethylene glycol-polypropylene glycol diacrylate, ethylene oxide adduct dimethacrylate of bisphenol A, ethylene oxide adduct diacrylate of bisphenol A, propylene oxide of bisphenol A Adduct dimethacrylate, propylene oxide adduct diacrylate of bisphenol A, etc., alone or in combination It can be used as a mixture.

  In order to polymerize such a monomer on the fiber surface and further improve the durability, pentaerythritol tetraacrylate may be used in combination.

  The present invention further includes a cellulose derivative in the coating.

  The cellulose derivative of the present invention is not particularly limited, but the weight average molecular weight of such a cellulose derivative is preferably from 100,000 to 100,000, more preferably from about 400 to 10,000, from the viewpoint of obtaining antifouling properties. If the molecular weight is less than 100, washing durability is difficult to obtain, and if it is greater than 100,000, the viscosity may be too high when it is dissolved, making it difficult to handle.

  In addition, such a cellulose derivative is preferably a water-soluble one obtained by methoxylation, hydroxyethoxylation or hydroxypropoxylation of a part of the hydroxyl group of cellulose. The substitution rate for the methoxy group, hydroxyethoxy group, and hydroxypropoxy group is preferably 10 to 50% of the total hydroxyl groups from the viewpoint of antifouling properties. It is also preferable to mix a crosslinking agent in order to crosslink the hydroxyl group and further improve the durability, and examples thereof include an epoxy crosslinking agent, an isocyanate crosslinking agent, and a melamine crosslinking agent.

The polymerizable monomer and the cellulose derivative are preferably used in a weight ratio of 1: 2 to 5: 1. When the cellulose derivative exceeds 1: 2, it is difficult to form a uniform film on the fiber, it is easy to fix in a block shape, dirt easily enters, and durable antistatic properties may not be obtained. On the other hand, when the amount of the polymerizable monomer exceeds 5: 1, it may be difficult to improve the antifouling property although the uniform film property and the antistatic property are improved.

From a polymer and a cellulose derivative comprising a polymerizable monomer having two or more acrylic groups and / or methacrylic groups as both ends or one end of the main chain or a side chain of the main chain mainly composed of a polyalkylene oxide segment In order to form a resin film, it is preferable to use a polymerization initiator for the monomer and the cellulose derivative. As the polymerization initiator, general vinyl polymerization initiators such as ammonium persulfate, potassium persulfate, azobisisobutyronitrile, ammonium sulfate, and the like can be used. The heat treatment for polymerization is preferably dry heat treatment or steam heat treatment at a temperature of 50 to 180 ° C. for 0.1 to 30 minutes, but steam heat treatment produces a uniform resin film on the fiber surface. It is easy to form and the texture after the resin film is formed is flexible, it is easy to uniformly coat the surface of the single fiber with resin, and the chance of direct contact between dirt and fibers is reduced. Saturated steam or superheated steam at a temperature of 80 to 160 ° C. is preferably used for the steaming heat treatment. More preferably, saturated steam at a temperature of 90 to 130 ° C. or superheated steam at a temperature of 110 to 160 ° C. is used, both of which perform the treatment for several seconds to several minutes.

After steaming and heat treatment, to remove unreacted monomers and polymerization catalyst and to ensure fastness to dyeing, use hot water washing at a temperature of 50 to 95 ° C, nonionic surfactant, sodium carbonate, etc. It is preferable to perform all washing. In the present invention, the resin film may be formed directly on the film, but it is also preferable that the resin film is fixed to the fiber surface in a layer form through a film made of a triazine ring-containing compound.

The triazine ring-containing compound used in the present invention is a compound containing a triazine ring and having at least two polymerizable functional groups. Examples of such triazine ring-containing compounds include the following general formula:

(Wherein, R0～R2 _{are, -H, -OH, -C 6 H} 5, -C n0 H 2n0 + 1 (n0: 1~2), - COOC n1 H 2n1 + 1 (n1: 1~20), - CONR3R4, -NR3R4 _{(However, R3, R4: -H, -OC} n3 H 2n3 + 1, -CH 2 COOC n3 H 2n3 +1 (n3: 1~20), - CH 2 OH, -CH 2 CH 2 OH, -CONH 2, _{-CONHCH 2 OH-O- (X-} O) n4 -R5 (X: C 2 H 4, C 3 H 6, C 4 H 8, n4: 1~1500, R5: -H, -CH 3, -C ₃ H ₇ )), and a compound obtained by adding a polymerizable functional group to the compound represented by).

  Specific examples of the compound include trimethylol melamine and hexamethylol melamine.

  Examples of the polymerizable functional group include an amino group, an amide group, a hydroxyl group, a phenyl group, an alkyl ester group, an alkoxymethyl group, a methylol group, an ethylol group, and an N-methylolamide group.

  Commercially available triazine ring-containing compounds include “Beccamin M-3” (manufactured by Dainippon Ink & Chemicals, Inc.), “UNIKA RESIN 380-K” (manufactured by Union Chemical Co., Ltd.), and “Riken Resin MM-35”. (Miki Riken Kogyo Co., Ltd.).

  The resin film containing the triazine ring-containing compound of the present invention is preferably formed uniformly on the surface of a single fiber.

  As a method for forming the resin coating, an aqueous solution composed of a triazine ring-containing compound and a polymerization catalyst is applied on the fiber, and then heat treatment is performed so as to polymerize.

  Examples of the polymerization catalyst include acids such as acetic acid, formic acid, acrylic acid, malic acid, tartaric acid, maleic acid, phthalic acid, sulfuric acid, persulfuric acid, hydrochloric acid, phosphoric acid, and ammonium salts, sodium salts, potassium salts, and magnesium salts thereof. One or more of these can be used. Of these, ammonium persulfate and potassium persulfate are preferably used as the catalyst. The polymerization catalyst is preferably used in a proportion of 0.1 to 20% by weight based on the amount of monomer used.

  The heat treatment for the polymerization of the triazine ring-containing compound is preferably a dry heat treatment or a steam heat treatment at a temperature of 50 to 180 ° C. for 0.1 to 30 minutes. It is easy to form a uniform resin film, and the texture after the resin film is formed is flexible, and it is easy to uniformly coat the surface of a single fiber with resin, thereby reducing the chance of direct contact between dirt and fibers. Saturated steam or superheated steam at a temperature of 80 to 160 ° C. is preferably used for the steaming heat treatment. More preferably, saturated steam at a temperature of 90 to 130 ° C. or superheated steam at a temperature of 110 to 160 ° C. is used, both of which perform the treatment for several seconds to several minutes.

  After steaming and heat treatment, to remove unreacted monomers and polymerization catalyst and to ensure fastness to dyeing, use hot water washing at a temperature of 50 to 95 ° C, nonionic surfactant, sodium carbonate, etc. It is preferable to perform all washing. Since the fiber structure of the present invention has excellent antistatic and antifouling properties, it is suitable for clothing applications such as work clothes and aprons where dirt easily adheres.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. Moreover, the quality evaluation in an Example was implemented with the following method.
<Electrical control>
Using the method specified in JIS L 1094B method (friction band voltage measurement method), measure the friction band voltage using cotton as the target fabric in an atmosphere of 20 ° C x 40% RH after 20 home washings. displayed. The larger the value, the worse the antistatic property.

<Anti-fouling>
The test procedure is as follows.
(1) Collect a 10 cm × 10 cm test piece.
(2) The test piece is placed on a 10 cm × 10 cm glass plate, 0.05 cc of B heavy oil is dropped on the center of the test piece, and a 1 mm thick 5 cm × 5 cm glass plate is placed on the glass. A 200 g load is placed on the plate and left for 1 minute.
(3) Remove the load and the glass plate, transfer the test piece onto the filter paper, cover it with tissue paper, wipe it with a roller to wipe off the dirt, and leave it in a horizontal state for 24 hours to dry naturally.
(4) Dissolve the test specimen after contamination in a self-reversing swirl electric washing machine with a weak alkaline synthetic detergent specified in JIS K337 (established in 1972, revised in 1994) to a concentration of 0.1% by volume. 25 L of the obtained liquid is washed for 5 minutes under strong conditions at a temperature of 40 ± 2 ° C. at a bath ratio of 1:50, then drained and washed with water for 5 minutes.
(5) Take out the test piece after washing without squeezing it, press lightly with filter paper to drain the water, and dry naturally in a horizontal state.
(6) Contamination of the dried test piece is determined on a gray scale, and “washing removal” (antifouling) is obtained. The grade is determined by a gray scale for contamination according to JIS L 0805 (established in 1965, revised in 2005). It shows that antifouling property is good as it goes from 1st grade to 5th grade. A weak alkaline synthetic detergent specified in JIS K 337 (established in 1972, revised in 1994) was dissolved in an automatic reversing swirl electric washing machine to a concentration of 0.1% by volume. At a temperature of ± 2 ° C., the sample was washed under strong conditions for 10 minutes, then drained and washed with overflow water for 10 minutes × 2 times. This was repeated 10 times, and then air-dried. The obtained laundry cloth was measured for antifouling property by the method described above, and the washing durability performance was evaluated.

[Example 1] After weaving a plain woven fabric using a 84 dtex, 36 filament twin yarn false twisted yarn made of polyethylene terephthalate as a warp yarn, and a 167 dtex, 72 filament twin yarn false twist yarn as a horizontal yarn, The obtained plain woven fabric was scoured at a temperature of 95 ° C. according to a conventional method using a continuous scourer, washed with hot water, then dried at a temperature of 130 ° C., and a pin tenter set at a temperature of 180 ° C. Next, the obtained plain woven fabric is dyed fluorescent white at a temperature of 130 ° C. using a liquid dyeing machine, washed in a conventional manner, washed with hot water, dried, and pinter set at a temperature of 170 ° C. ( A dyed fabric having a length / width) density (83/55) /2.54 cm was prepared and used as a test cloth.

The obtained sample cloth was dipped in the following processing liquid, drawn with mangle so that the drawing rate was 90% by weight, and then treated for 5 minutes in a saturated steam atmosphere at a temperature of 104 ° C.

(A) Polymerizable monomer polyethylene glycol dimethacrylate 20 g / l
(Polyalkylene oxide segment molecular weight 1000, active ingredient 100% by weight)
(B) Catalyst Ammonium persulfate 2 g / l
(C) Cellulose derivative “Marporose M400” (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) (preparing 3% by weight solution) 100 g / l

Subsequently, it was washed with hot water at a temperature of 70 ° C., washed with water, and dried at a temperature of 130 ° C. to obtain a processed product.

  The obtained processed product showed high antistatic property and dirt removal property even after washing. The evaluation results are shown in Table 1.

[Example 2]
The sample cloth was immersed in the following processing solution, drawn with mangles so that the drawing rate was 90% by weight, and then treated for 5 minutes in a saturated steam atmosphere at a temperature of 104 ° C.

(A) Polymerizable monomer polyethylene glycol dimethacrylate 20 g / l
(Polyalkylene oxide segment molecular weight 1000, active ingredient 100% by weight)
(B) Catalyst Ammonium persulfate 2 g / l
(C) Cellulose derivative “Metroze 60SH-4000” (manufactured by Shin-Etsu Chemical Co., Ltd.) (Create a 3 wt% solution)
100 g / l

Subsequently, it was washed with hot water at a temperature of 70 ° C., washed with water, and dried at a temperature of 130 ° C. to obtain a processed product.

The obtained processed product showed high antistatic property and dirt removal property even after washing. The evaluation results are shown in Table 1.
[Example 3]
The sample cloth was immersed in the following processing solution, drawn with mangles so that the drawing rate was 90% by weight, and then treated for 5 minutes in a heated steam atmosphere at a temperature of 150 ° C.

(A) Polymerizable monomer polyethylene glycol dimethacrylate 10 g / l
(Polyalkylene oxide segment molecular weight 1000, active ingredient 100% by weight)
(B) Catalyst Ammonium persulfate 2 g / l
(C) Cellulose derivative “Marporose M400” (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) (preparing 3% by weight solution) 200 g / l

Subsequently, it was washed with hot water at a temperature of 70 ° C., washed with water, and dried at a temperature of 130 ° C. to obtain a processed product.

The obtained processed product showed high antistatic property and dirt removal property even after washing. The evaluation results are shown in Table 1.
[Example 4]
The sample cloth was dipped in the following processing liquid, mangled so that the amount of the aqueous solution adhered was 90% by weight, and then treated for 5 minutes in a saturated steam atmosphere at a temperature of 104 ° C.
(A) “Beckamine M-3”
(Dainippon Ink & Chemicals, Inc. Triazine ring-containing compound (trimethylol melamine having an amino group), solid content 80% by weight) 30 g / l
(B) Catalyst Ammonium persulfate 3 g / l

Subsequently, it was washed with hot water at a temperature of 70 ° C., washed with water, and dried at a temperature of 130 ° C.

Subsequently, the process similar to Example 1 was performed and the processed product was obtained.
The obtained processed product showed high antistatic property and dirt removal property even after washing. The evaluation results are shown in Table 1.

[Comparative Example 1]
The sample cloth was immersed in the following processing solution, drawn with mangles so that the drawing rate was 90% by weight, and then treated for 5 minutes in a saturated steam atmosphere at a temperature of 104 ° C.

(A) Polymerizable monomer polyethylene glycol dimethacrylate 20 g / l
(Polyalkylene oxide segment molecular weight 1000, active ingredient 100% by weight)
(B) Catalyst Ammonium persulfate 2 g / l

Subsequently, it was washed with hot water at a temperature of 70 ° C., washed with water, and dried at a temperature of 130 ° C. to obtain a processed product.

The obtained processed product showed high antistatic properties even after washing, but the performance of removing stains was low. The evaluation results are shown in Table 1.
[Comparative Example 2]
Immerse the sample fabric in the following processing solution, squeeze with mangle so that the squeezing rate is 90% by weight, and then dry it by dry heat treatment at 130 ° C, then set it at 160 ° C for 1 minute to obtain a processed product. It was. (A) Cellulose derivative “Marporose M400” (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) (preparing 3% by weight solution) 100 g / l

The obtained processed product has a hard texture and is not suitable as a clothing product, and has low antistatic and antifouling effects and low washing durability.

The evaluation results are shown in Table 1. [Comparative Example 3]
The dyed cloth was used for the antistatic and antifouling evaluation as it was. Both effects were low. The results are shown in Table 1.

  The fiber structure of the present invention is a fiber structure having excellent antifouling properties that can easily remove dirt once adhered by washing and also has antistatic properties.

Claims (4)

  A polymerizable monomer having a polymerizable monomer having two or more acrylic groups and / or methacrylic groups as both ends or one end of a main chain mainly composed of a polyalkylene oxide segment or a side chain of the main chain and a cellulose derivative as a polymerization component The fiber structure which has the resin film formed by superposing | polymerizing on a fiber on the fiber surface.   The fiber structure according to claim 1, wherein the cellulose derivative is obtained by methoxylation, hydroxyethoxylation or hydroxypropoxylation of a part of cellulose hydroxyl group.   The fiber structure according to claim 1 or 2, wherein the weight ratio of the polymer to the cellulose derivative is 1: 2 to 5: 1.   The fiber structure according to any one of claims 1 to 3, wherein the coating is fixed to the fiber surface in a layered manner through a coating composed of a triazine ring-containing compound.