WO2004025016A1

WO2004025016A1 - Modified fabric and process for its production

Info

Publication number: WO2004025016A1
Application number: PCT/JP2002/009431
Authority: WO
Inventors: Shuichi Murakami; Ryosei Takigaura; Koji Nakade
Original assignee: Komatsu Seiren Co., Ltd.
Priority date: 2002-09-13
Filing date: 2002-09-13
Publication date: 2004-03-25
Also published as: AU2002338066A1; JP4319621B2; JPWO2004025016A1

Abstract

A modified fabric, characterized by being produced by polymerizing, on a fabric, (X) a monomer having a phosphorylcholine-analogous group selected from between 2-acryloyloxyethylphosphorylcholine and 2-methacryloyloxy- ethylphosphorylcholine and/or a polymer thereof with (A) a bifunctional monomer represented by the general formula (1), (B) a monomer having a group selected from among hydroxyl, carboxyl, amino, sulfonic acid group, and phosphoric acid group, and (C) a monomer having at least one aziridinyl group. (1) The modified fabric is excellent not only in feelings such as softness and drape property but also in water- and moisture -absorbing properties and endurance and exhibits high skin-care effect. The modified fabric can be favorably used particularly for goods to come into direct and continuous contact with the skin, for example, underwear, clothes, gloves, hosiery, and bedclothes.

Description

Description: Modified fiber fabric and method for producing the same

TECHNICAL FIELD The present invention relates to a modified fiber fabric suitable for use in direct contact with the skin and a method for producing the same. In particular, it has high water absorption and hygroscopicity, excellent sweat and other absorbency, excellent durability, and also has a skin care effect (moisturizing effect on skin, etc.) while maintaining softness and drape-like texture. The present invention relates to a mild fiber fabric and a method for producing the same. Background art

A number of techniques have been proposed for attaching various surfactants to the surface of a fiber cloth to increase water absorption and hygroscopicity, to avoid discomfort due to sweat and the like, and to carry out antifouling processing. For example, Japanese Patent Application Laid-Open No. 63-16666 discloses a treatment for adhering an aliphatic ester type nonionic surfactant to a fiber cloth. The gazette discloses a treatment for attaching a sorbitan alkyl fatty acid ester to a fiber fabric. '

However, in all of the fiber fabrics subjected to these treatments, the surfactant is liable to fall off by washing or the like. As a result, it is not possible to maintain water absorption and hygroscopicity over a long period of time, and the durability is insufficient. In addition, surfactants have low affinity for the skin and are not sufficiently concerned about skin irritation.

Therefore, as a means for performing a durable water-absorbing treatment on a fiber cloth, a technique of polymerizing various monomers such as BULLMONOMETER on the fiber cloth has been disclosed (for example, Japanese Patent Application Laid-Open No. 58-16 / 1983). Japanese Patent Application Laid-Open No. 9-569, Japanese Patent Application Laid-Open No. 08-48735, Japanese Patent Application Laid-Open No. 08-209540, etc.). In addition, by using a cross-linked vinyl sulfonic acid polymer and a chemical such as a modified organosilicate to polymerize on a fiber cloth, a durable water-absorbing treatment is performed, and at the same time, an antifouling (blackening prevention) process is performed. It is disclosed that it can be applied (Japanese Patent Application Laid-Open No. 11-161647). These treatments are mainly intended to impart water absorbency and hygroscopicity to the fiber fabric by polymerizing an acryl-based monomer on the fiber fabric. However, remarkable water absorption and hygroscopicity cannot be imparted by such treatment. In addition, skin care effects (moisturizing effects on skin, etc.) cannot be expected. On the other hand, a phosphorylcholine-like group-containing compound, 2_ (meth) acryloyloxhetinolephosphorylcholine ゃ 2-metacloinoleoxyethylphosphorylcholine, has a structure similar to phospholipid (phosphatidylcholine), which is the main component of biological membranes. It is known to have excellent biocompatibility (blood compatibility, non-adsorption of biomaterials, etc.) (Japanese Patent Publication No. 60-21599, etc.). It is also known that these compounds have antifouling properties and moisturizing properties.

For example, in the field of cosmetics, humectants such as biopolymers and sodium hyaluronate, and oils such as animal and vegetable oils have been blended into various cosmetics for the purpose of preventing rough skin. It has been reported that the above phosphorylcholine analog-containing compound has a skin care effect and can be used as a humectant (see, for example, JP-A-09-31595, JP-A-09-31). No. 549 publication).

Against this background, for the purpose of imparting a skin care effect to a fiber fabric, a treatment of contacting the above phosphorylcholine-containing group-containing compound with the fiber fabric has been proposed (Japanese Patent Application Laid-Open No. 2001-200480). Publication, Japanese Patent Application Laid-Open No. 2002-146466 Publication).

However, in such treatment, although a slight improvement in water absorption and hygroscopicity is recognized, the phosphorylcholine-like group-containing compound adheres only to the surface of the fiber cloth, so that high water absorption and hygroscopicity can be obtained. Absent. In particular, remarkable water absorption and hygroscopicity cannot be imparted to a hydrophobic synthetic fiber cloth. In addition, if the concentration of the phosphorylcholine-like group compound is increased and the amount of the phosphorylcholine-like compound is increased and the amount of the phosphorylcholine-like compound is increased, a so-called glued state is obtained, which hinders the texture such as flexibility and drapability. Although durability (washing resistance, etc.) has not been verified at all, durability cannot be expected simply by attaching a phosphorylcholine-like group-containing compound to the surface of a fiber cloth. DISCLOSURE OF THE INVENTION 本 The present invention is a low-irritant modification having excellent water absorbency, excellent durability (washing resistance, etc.), and also a skin care effect, while ensuring the texture such as flexibility and drapability. It is an object to provide a fiber fabric and a method for producing the same.

The inventor conducted intensive studies to achieve such an object, and as a result, introduced a phosphorylcholine-like group-containing compound into the fiber as well as into the fiber by polymerizing the fiber with a specific fiber treatment solution on the fiber cloth. And found that the present invention was completed. The fiber treatment liquid used is also new. The modified fiber fabric of the present invention is characterized in that 2- (meth) atalyloyloxyphosphorylphosphorylcholine or 2-methacryloxyshethylphosphorylcholine is formed on the fiber cloth. Or a component (X) that is a polymer thereof, a component (A) that is a bifunctional monomer represented by the following general formula (1), a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and a phosphate group. It is characterized by being obtained by polymerizing a component (B) which is a monomer containing any of these groups and a component (C) which is a monomer containing at least one aziridine group.

Z CH ₃ CH ₃ Z

CH ₂ = C— CO0 (CH ₂ CH ₂ 0) _a (CH ₂ »CH0) x— R— (0CHCH ₂ ) _y (0CH ₂ CH ₂ ) _b 00C C = CH2

• '• (1)

(However, in the equation (1), R is

C _n H _{2 n} — (where n represents an integer of 1 to 6). Z represents a hydrogen atom or a methyl group. a and b represent a positive integer in which a + b is in the range of 0 to 50, and X and y represent 0 or a positive integer in which x + y is in the range of 0 to 30. A + b + x + y is 10 or more. ) According to the present invention, it is possible to provide a modified fiber cloth in which the component (X) and the components (A) to (C) are introduced into the inside of the surface of the fiber. Further, according to the present invention, it is possible to provide a modified fiber cloth in which the component (X) and the components (A) to (C) are graft-polymerized on a fiber cloth. Here, a modified fiber cloth in which the component (X) is introduced into the surface and inside of the fiber and a modified fiber cloth in which the component (X) is graft-polymerized to the fiber cloth are also novel. Fiber fabrics are also included in the present invention. The fiber treatment liquid of the present invention is characterized by containing the component (X) and the components (A) to (C).

The first method for producing a modified fiber fabric of the present invention includes: a liquid contacting step of bringing the fiber treatment liquid of the present invention into contact with a fiber fabric; and a component (X) and a component (A) to

(C) a polymerization step of polymerizing (C).

The method for producing a modified fiber fabric according to the second aspect of the present invention includes: a first liquid contacting step of bringing a fiber treatment liquid containing the components (A) to (C) into contact with the fiber cloth; A) a first polymerization step of polymerizing (A) to (C); a second liquid contacting step of bringing a solution of component (X) into contact with a fiber cloth obtained by polymerizing components (A) to (C); Ingredients on fabric

And a second polymerization step of polymerizing (X).

By these production methods, the above-mentioned modified fiber fabric of the present invention in which the component (X) and the components (A) to (C) are polymerized can be produced. In the first production method, the component (X) and the components (A) to (C) are simultaneously polymerized, whereas in the second production method, the components (A) to (C) are polymerized. Thereafter, component (X) is polymerized. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a diagram showing evaluation results of Example 1 and Comparative Examples 1 and 2 according to the present invention. FIG. 2 is a diagram showing evaluation results of Example 1 and Comparative Examples 1 and 2 according to the present invention. FIG. 3 is a diagram showing evaluation results of Example 2 and Comparative Example 3 according to the present invention. FIG. 4 is a diagram showing evaluation results of Example 2 and Comparative Example 3 according to the present invention. FIG. 5 is a diagram showing evaluation results of Example 3 and Comparative Examples 4 and 5 according to the present invention. FIG. 6 is a diagram showing evaluation results of Example 3 and Comparative Examples 4 and 5 according to the present invention. FIG. 7 is a diagram showing evaluation results of Example 4 and Comparative Example 6 according to the present invention. FIG. 8 is a diagram showing evaluation results of Example 4 and Comparative Example 6 according to the present invention. FIG. 9 is a diagram showing evaluation results of Example 5 and Comparative Examples 7 and 8 according to the present invention. FIG. 10 is a diagram showing evaluation results of Example 5 and Comparative Examples 7 and 8 according to the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

[Modified fiber cloth]

The modified fiber fabric according to the present invention comprises, on the fiber fabric, a phosphorylcholine-like group-containing monomer selected from 2- (meth) atalyloyloxyethyl phosphorylcholine or 2-methacryloxyshethylphosphorylcholine and / or Component (X) which is a polymer, component (A) which is a bifunctional monomer represented by the following general formula (1), any of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and a phosphate group The component (B) which is a monomer containing such a group and the component (C) which is a monomer containing at least one aziridine group are polymerized.

Z CH ₃ CH ₃ Z

CH ₂ = C C00 (CH ₂ CH20) _a (CH2 CH0) x »R (0CHCH2) _y (0CH2CH ₂ ) _b 00C» C = CH ₂

'•' (1)

(However, in the equation (1), R is

_ C _n H _{2 n} — (where n represents an integer of 1 to 6). Z represents a hydrogen atom or a methyl group. a and b are positive integers where a + b is in the range of 0 to 50, and X and y are 0 or positive integers in which x + y is in the range of 0 to 30. Represents a number. A + b + x + y is 10 or more. The term “polymer of a phosphorylcholine-like group-containing monomer” refers to a homopolymer of a phosphorylcholine-like group-containing monomer or a copolymer of a phosphorylcholine-like group-containing monomer with another monomer. Shall be included. The modified fiber fabric of the present invention includes (i) a fiber fabric obtained by graft-polymerizing the component (X) and the components (A) to (C); and (ii) a component (X) and a component (X) on the fiber fabric. The homopolymers of components (A) to (C) and those in which Z or a copolymer in which a plurality of these are copolymerized are produced; and (iii) the component of part (iii) is graft-polymerized to the fiber cloth, and the remaining Includes those where the components have formed homopolymers and / or copolymers on fiber fabrics. Among these, (i) those obtained by graft-polymerizing the component (X) and the components (A) to (C) on the fiber fabric are particularly preferable. The constituent fibers of the fiber fabric serving as the base material are not particularly limited, but natural fibers such as cotton, wool, silk, and hemp, and synthetic fibers such as nylon, acrylic, polyester, polypropylene, polyethylene, and polytrimethylene terephthalate; or Blended fibers and composite fibers of a plurality of types selected from these are exemplified. The present invention has a particularly remarkable effect on polyamide fibers such as nylon, polyester fibers, blended fibers containing these fibers (for example, blended fibers made of polyester / cotton, etc.), and fabrics made of composite fibers. Play. These fabrics have high hydrophobicity, and it is difficult to impart water absorbency and moisture absorbency by ordinary treatment. However, the present invention can effectively impart water absorbency and moisture absorbency to these fabrics. it can.

The form of the fiber cloth is not particularly limited, and examples thereof include a woven fabric, a knitted fabric, and a nonwoven fabric. In addition, scouring, dyeing, antibacterial processing, SR processing, flameproofing processing, antistatic processing and the like may be performed. Further, it may be processed into a product such as clothing, or may be before processed. Component (X) used in the present invention is a known compound, and is used for cosmetics, various medical materials, It is used for contact lenses and the like. Component (X) is a zwitterionic compound having both an anion group and a thione group in the molecule. Therefore, it is very hydrophilic and has high water retention properties, and when added to an aqueous solution, has the property of significantly reducing the surface tension of the aqueous solution. Furthermore, since it has a plurality of elements P and N having an unpaired electron pair in the molecule, it is easy to settle on the fiber cloth regardless of the type of fiber cloth, and is very detached once it is fixed and fixed on the surface. It has the property of being difficult. In addition, the component (X) has the same structure as the polar group of the phospholipid (phosphatidylcholine), which is the main component of the biological membrane, and has excellent affinity with the living body. Here, phosphatidylcholine is a constituent of living cells and is widely distributed in the animal and plant kingdoms.When ribosomes are formed in water, it binds to about 10 water molecules per phosphatidylcholine molecule in the lamellar layer. It is known to Phospholipids represented by lecithin are components similar to cell membranes and have high affinity for skin. In the cosmetics field, they are formulated for the purpose of alleviating rough skin and softening skin. Next, other components used in combination with the component (X) will be described.

The component (A) is not particularly limited as long as it is a bifunctional monomer represented by the general formula (1), and specific examples thereof are represented by the following general formulas (2) to (5) And the like.

CH ₃ CH ₃

i f

CH ₂ = C— C00 (CH ₂ CH ₂ 0) ₄ 0C— C = CH ₂ * "(2)

CH ₂ = CH— {X CH ₂ CH ₂₀ ) 230C— CH = CH _2- (5) Component (B) is a hydroxyl, carboxyl, amino, sulfonic, or phosphate group The monomer is not particularly limited as long as it is a monomer containing, but specific examples thereof include acrylic acid, methacrylic acid, styrene sulfonic acid, maleic acid, itaconic acid, knoletonic acid, bininolenolephonic acid, and 2-aryloxy. 2-Hydroxypropanesnolefonic acid, 2-acrylamide 2-methylpropanesulfonic acid, 2-hydroxylethyl methacrylate, hydroxypropyl methacrylate, the following general formula (6)

And the like.

CH ₂ '"(6)

(In the formula (6), c and d each represent 0 or a positive integer such that c + d is 5 or more.)

CH ₃₀

CH = C — C0CXCH CH CH 0) P ™ 0H * "(7)

I

0H

(In the formula (7), e represents an integer of 5 or more.)

CH ₃ 0 CH ₂ = CHC P— OH ", (8) OH The component (C) is not particularly limited as long as it is a monomer containing one aziridine group or a polyfunctional monomer containing two or more aziridine groups. Specific examples thereof include compounds represented by the following general formulas (9) to (13).

'(Ten)

Since the modified fiber fabric of the present invention incorporates the component (X), it has the properties of the component (X), that is, it has properties of water absorption and hygroscopicity and excellent skin care effect.

Further, the present inventor has proposed that component (X) and components (A) to (C) are used in combination.

1

It has been found that the polymerization reaction of the component (X) can be promoted, and the component (X) can be effectively introduced not only into the surface of the fiber but also into the interior of the fiber. The modified fiber cloth in which the component (X) is introduced not only into the surface of the fiber but also into the interior of the fiber does not have a so-called glued state as compared with a fabric in which the component (X) adheres only to the surface of the fiber. In addition, while maintaining the texture such as flexibility and drapability, it has remarkably excellent water absorption and hygroscopicity, and the component (X) hardly elutes or desorbs in water, and the durability is remarkably excellent. In particular, in the case where the component (X) is graft-polymerized to the fiber cloth, the component (X) is strongly bonded to the fiber cloth, so that the component (X) is introduced into the fiber, Even higher durability can be realized. The modified fiber cloth in which the component (X) is introduced into the surface and inside of the fiber and the modified fiber cloth in which the component (X) is graft-polymerized to the fiber cloth are also novel.

In addition, the components (A) to (C) used in combination with the component (X) are also excellent in water absorption and hygroscopicity, and these components readily diffuse into the fiber and polymerize. Therefore, by polymerizing the components (A) to (C), the components (A) to (C) having excellent water absorption and hygroscopicity can be introduced not only to the surface of the fiber but also to the inside. Therefore, higher water absorption and hygroscopicity can be obtained than when component (X) is used alone. In addition, the components (A) to (C) introduced into the fiber are not easily detached and have excellent durability. In particular, those in which these components are graft-polymerized are firmly bonded to the fiber cloth, so that higher durability can be realized in combination with being introduced inside the fibers. Therefore, the modified fiber fabric of the present invention, obtained by polymerizing the component (X) and the components (A) to (C) on the fiber fabric, can absorb water from the surface of the fiber to the inside while maintaining the texture. · Hydrogen-absorbing treatment, water absorption · Excellent moisture absorption, extremely excellent durability, and high skin care effect.

According to the modified fiber fabric of the present invention, sweat and the like can be quickly absorbed even during periods of heavy sweating, such as during sports or summertime, and at bedtime, so that the user can feel refreshed. . In addition, it is possible to provide skin care effects such as moisturizing the skin and promoting natural healing of the rough skin, even for users with sensitive skin.

[Method for producing modified fiber fabric]

Next, a method for producing the modified fiber fabric of the present invention will be described.

(First manufacturing method)

The first production method of the present invention is characterized in that component (X) and components (A) to (C) are simultaneously polymerized on a fiber cloth. That is, a liquid contacting step of bringing a fiber treatment liquid containing the component (X) and the components (A) to (C) into contact with the fiber cloth, and the polymerization of the component (X) and the components (A) to (C) on the fiber cloth And a polymerization step of causing the polymerization. In addition, the fiber treatment liquid used in the first production method of the present invention is also novel, and by using this, the above-described modified fiber cloth of the present invention can be easily produced. The concentration of the component (X) in the fiber treatment liquid is not particularly limited, and is appropriately set depending on the fiber cloth to be used, but is preferably about 0.01 to 10.0% by mass. When the concentration of the component (X) is less than 0.01% by mass, it takes a long time to fix (polymerize) the component (X) to the fiber cloth. If the concentration of the component (X) is more than 10.0% by mass, the viscosity of the fiber treatment liquid increases, and the fixing (polymerization) of the component (X) to the fiber cloth may become non-uniform, and unreacted. Compounds may remain and may affect the texture.

The concentration of the component (A) in the fiber treatment liquid is not particularly limited, but is preferably about 1 to 20% by mass. The mixing ratio of the components (A), (B) and (C) is not particularly limited, either, but is preferably 1: 0.01-1: 0.01-1. The solvent used for the fiber treatment liquid is not particularly limited, but water and organic solvents (alcohols, dimethylformamide, acetone, dimethylsulfoxide, etc.) can be used. One type of solvent may be used alone, or two or more types may be used in combination. Among them, an aqueous solvent is preferably used as the solvent because it has little irritation to the skin and a small effect on the living body.In particular, water Z or an aliphatic lower alcohol having 1 to 3 carbon atoms is preferably used. preferable. Examples of the aliphatic lower alcohol having 1 to 3 carbon atoms include methyl alcohol, ethyl alcohol, and isopropyl alcohol, and these may be used alone or in combination of two or more. good. Further, the fiber treatment liquid may be added with various additives in addition to the components (X), (A) to (C) and the solvent. For example, a reactive resin such as a melamine resin, a dalioxal resin, an epoxy resin, or the like, a crosslinking agent such as a dimine crosslinking agent is added, and the components (X) and components (A) to (C) are added. At the time of polymerization, these may be crosslinked. Further, a polymerization initiator such as potassium peroxide, ammonium persulfate, hydrogen peroxide, benzoylperoxide, azobisisobuty-trinole, tertiary butyl peroxide, and the like may be added. In order to exhibit a higher moisturizing effect, natural polymers such as sericin, silk fiproin, collagen, and protein may be added.

For example, the fiber treatment liquid may be prepared by dissolving the component (X) in an aqueous solvent (eg, water and Z or an aliphatic lower alcohol having 1 to 3 carbon atoms) and the components (A) to (C). It can be prepared by adding various additives accordingly. The method for bringing the fiber treatment liquid into contact with the fiber cloth is not particularly limited, and examples thereof include an immersion treatment method and a padding method. For example, in the padding method, after the fiber treatment liquid is brought into contact with the fiber cloth, the fiber cloth is squeezed as necessary, and the amount of the fiber treatment liquid is adjusted. Further, if necessary, heat and dry (dry heat treatment) at about 50 to 130 ° C. The polymerization reaction does not easily proceed only by the dry heat treatment.

After the above treatment, polymerization is performed. The polymerization of the component (X) and the components (A) to (C) is performed on the fiber cloth to which the fiber treatment liquid is attached, such as a wet heat treatment, an electron beam irradiation treatment, an ultraviolet irradiation treatment, and a microwave irradiation treatment. Can be performed. When using a wet heat treatment, for example, 90 to 140 ° C filled with steam What is necessary is just to process for about 1 to 90 minutes in a moderate atmosphere. When using electron beam irradiation, ultraviolet irradiation, or microwave irradiation, electron beam, ultraviolet, or microwave irradiation may be performed before the liquid contacting step. Irradiation may be performed after the liquid contacting step. In addition, when using electron beam irradiation, ultraviolet irradiation, or microwave irradiation, replacing the surrounding atmosphere with nitrogen or the like during the polymerization reaction prevents the generated radicals from disappearing and prevents the polymerization components from becoming effective. This is preferable because the utilization can be improved.

In the present invention, in this step, the polymerization reaction proceeds not only on the surface of the fiber but also inside the fiber. In the production method of the present invention, (i) the case where the component (X) and the components (A) to (C) are graft-polymerized to the fiber cloth; and (ii) the component (X) on the fiber cloth. And the case where a homopolymer of the components (A) to (C) and / or a copolymer obtained by copolymerizing a plurality of these are produced; and (iii) some components are graph-polymerized on the fiber cloth and the remaining components are Produces homopolymers and / or copolymers on fiber fabrics. However, (i) component (X) and component

It is preferred that (A) to (C) are graft-polymerized.

After the completion of the polymerization reaction, washing is preferably performed to remove unreacted compounds adhering to the fiber cloth.

In the production method of the present invention, a known antibacterial agent, SR agent, flame retardant, antistatic agent, or the like can be added to the fiber fabric before the liquid contacting step or after the polymerization step. is there.

(Second manufacturing method)

The second production method of the present invention is characterized in that after the components (A) to (C) are polymerized on the fiber cloth, the component (X) is polymerized. That is, a first liquid contacting step of bringing a fiber treatment liquid containing the components (A) to (C) into contact with the fiber cloth;

A first polymerization step of polymerizing (A) to (C), a second liquid contacting step of bringing a solution of component (X) into contact with a fiber cloth obtained by polymerizing components (A) to (C), A second polymerization step of polymerizing the component (X) on the fiber cloth. Here, a fiber treatment solution containing the components (A) to (C) or a solution of the component (X) is used. As the solvent, the same solvent as the fiber treatment liquid used in the above-mentioned first production method of the present invention can be used.

In addition, the method for preparing a fiber treatment solution containing the components (A) to (C), the method for bringing the fiber treatment solution into contact with the fiber cloth, and the method for polymerizing the components (A) to (C) do not use the component (X). Except for this, it is the same as the first manufacturing method described above. In addition, component to fiber fabric

The method of contacting the solution of (X) and the method of polymerizing the component (X) on the fiber cloth include the method of contacting the fiber cloth with a fiber treatment solution containing the components (A) to (C),

It is the same as the polymerization methods (A) to (C). According to the first and second production methods of the present invention, the modified fiber of the present invention has extremely good water absorbency and moisture absorbency, extremely excellent durability, and a high skin care effect, while maintaining the texture. It is possible to easily manufacture a yarn zen cloth.

The polymerization promoting effect of the component (X) can also be obtained by the second production method in which the components (A) to (C) are polymerized and then the component (X) is polymerized on the fiber cloth. X) can be introduced not only on the surface of the fiber but also inside the fiber. However, the first production method in which the component (X) and the components (A) to (C) are simultaneously polymerized on the fiber fabric has a higher effect of promoting the polymerization of the component (X), and has higher water absorption and moisture absorption. It is possible to produce a modified fiber fabric having excellent properties and durability. In addition, the first manufacturing method is preferable in terms of a small number of steps.

Example

Next, examples and comparative examples according to the present invention will be described. In each case, fiber fabrics including modified fiber fabrics were produced and evaluated.

(Evaluation items and evaluation methods)

Evaluation items and evaluation methods were as follows.

The prepared fiber cloth was cut into 1 cm x 1 cm, degreased with acetone, and subjected to surface analysis with an X-ray photoelectron spectrometer (ESCA3300, manufactured by Shimadzu Corporation) to determine the phosphorus introduced into the fiber cloth. As an evaluation of the amount of lipid components, the P / C atomic ratio was measured. The detection limit of the equipment used was 0.03%.

A weak surface roughness was generated with a mixed solvent of acetone and ether, and the produced fiber fabric was brought into contact with the portion where the surface roughness was generated. Immediately before rough skin, immediately after rough skin, and three hours after contact with the fiber cloth, the amount of water evaporation (TEWL) is measured from the skin, and the skin care index is defined by the following formula. I asked. TEWL was measured using Tewameter TM210 (manufactured by Courage Khazaka).

Skin care index = (T EWL 3 hours after contact with test fabric—T EWL immediately before rough skin) / (TEWL immediately after rough skin—TEWL immediately before rough skin) X I 00 (%)

20. Apparatus for measuring heat and moisture transfer characteristics of clothing materials (TH Permeability Tester, manufactured by Toyo Seiki Seisaku-sho, Ltd.). C, an environment of 65% RH was used, and a change in humidity in the produced fiber fabric was measured. In this test, the higher the rate of decrease or the rate of decrease in humidity, the higher the moisture absorption and regeneration of the fiber fabric. Durability>

The evaluation of the amount of the phospholipid component, the skin care effect, and the hygroscopicity was performed twice in total at an initial stage (before washing) and after washing 20 times, and the durability was evaluated.

The washing was performed as follows based on the washing test JISL-0 21 17 03 method.

Pour water at a liquid temperature of 40 ° C up to the water level line indicating the standard amount of water in the water tank of the test equipment, and add a synthetic detergent for washing to the standard amount of water and dissolve it to make the washing liquid. A sample is put into the washing solution so that the bath ratio becomes 1:30, and the operation is started. After 5 minutes of treatment, stop the operation, dehydrate the sample with a dehydrator, and then change the washing liquid to fresh water at 30 ° C or less, and rinse for 2 minutes at the same bath ratio. After rinsing for 2 minutes, stop operation, dehydrate the sample, rinse again for 2 minutes, dehydrate, and hang or lay flat without direct sunlight. Then, if necessary, dry iron finish at the appropriate temperature of the material fiber.

(Example 1)

A ponge fabric using a polyester flammable yarn having a fabric weight of 110 gm ² was subjected to relaxation, scouring, presetting, alkali weight reduction processing, and dyeing in a conventional manner. Using this fiber fabric as a substrate, a modification treatment was performed.

A fiber treatment solution having the composition shown in Table 1 was prepared and applied to a fiber fabric by a padding method. The drawing ratio was 60% by mass. Thereafter, a wet heat treatment for 5 minutes with steam at 110 ° C. and 98% RH was performed to perform polymerization. After the completion of the polymerization reaction, washing and finishing were performed. The resulting modified fiber fabric was evaluated. Composition of fiber treatment liquid (Example 1)

(Comparative Example 1)

Using the same polyester ponge fabric as in Example 1, relaxing, scouring, presetting, alkali weight reduction processing, dyeing, and finishing set are performed in order by the usual method.

100% of taffeta fabric was obtained. The obtained fiber cloth was evaluated. (Comparative Example 2)

A modified fiber fabric was obtained in the same manner as in Example 1 except that a fiber treatment solution having the composition shown in Table 2 was prepared. The resulting modified fiber fabric was evaluated. Table 2 Composition of fiber treatment solution (Comparative Example 2)

(Evaluation results of Example 1 and Comparative Examples 1 and 2)

Table 3, FIG. 1 and FIG. 2 show the PZC atomic ratio, skincare index, and hygroscopicity test results of the fiber cloths obtained in Example 1 and Comparative Examples 1 and 2, respectively.

In Example 1 in which the component (X) and the components (A) to (C) were polymerized and modified on the fiber fabric, as shown in Table 3, the initial P / C atoms of the obtained modified fiber fabric were The number ratio was 0.58%, and it was confirmed that the component (X) which is a phospholipid was introduced. Further, even after washing 20 times, the decrease in the P / C atomic ratio was small, and it was confirmed that the component (X) was fixed in a state where it was difficult to desorb. This is because component (X) was introduced not only on the surface of the fiber but also inside. The texture of the modified fiber fabric such as flexibility and drapability was also good. Further, as shown in FIGS. 1 and 2, the modified fiber fabric exhibited a high skin care effect and a high hygroscopicity both at the initial stage and after washing 20 times. In addition, the modified fiber fabric obtained in Example 1 was initially and after washing 20 times. In both cases, there was no significant change in properties, and the durability was excellent.

On the other hand, in Comparative Example 1 in which the hydrophilization treatment was not performed, the obtained fiber fabric was significantly inferior in both skin care effect and hygroscopicity to Example 1. In Comparative Example 2 in which only the component (X) was polymerized and modified on the fiber cloth, the initial P / C atomic ratio of the obtained modified fiber cloth was 0.50%, It was confirmed that the component (X) was introduced. However, after washing 20 times, the atomic ratio of PZC decreased remarkably, and most components (X) were eliminated by the washing. This is because component (X) was introduced only on the surface of the fiber. Further, since the component (X) was introduced only into the surface of the fiber, the initial hygroscopicity was significantly inferior to that of Example 1. In addition, this modified fiber fabric obtained a high skin care effect at the initial stage, but after washing 20 times, the skin care effect was greatly reduced with the elimination of the component (X). Thus, the fiber fabric obtained in Comparative Example 2 was insufficient in hygroscopicity and durability. Table 3

(Example 2)

Using a polyester false twisted yarn having a fabric weight of 150 g / m ² , a 28 gauge interlock knit was produced. The polyester knit was subjected to relatas, scouring, presetting, and dyeing in a conventional manner. Using this fiber fabric as a substrate, a modification treatment was performed.

The same fiber treatment liquid as in Example 1 was applied to the fiber cloth by the padding method. Drawing ratio was 8 0 mass ^_0/0. Next, after drying at 120 ° C. for 3 minutes, a wet heat treatment was performed for 60 minutes with steam at 105 ° C. and 97% RH to carry out polymerization. After the completion of the polymerization reaction, a finishing set was performed. The resulting modified fiber fabric was evaluated. (Comparative Example 3)

Using the same polyester knitted fabric as in Example 2 (28-gauge interlocked knitted fabric using polyester false twisted yarn), relax, scour, preset, dye, and finish set were sequentially performed in the usual manner. A knit of 0% was obtained. The obtained fiber fabric was evaluated. ―

(Evaluation results of Example 2 and Comparative Example 3)

Table 4, FIG. 3, and FIG. 4 show the PZC atomic ratio, the number of days of sono r, and the results of the hygroscopicity test of the fiber fabrics obtained in Example 2 and Comparative Example 3, respectively.

In Example 2 in which the component (X) and the components (A) to (C) were polymerized and modified on the fiber cloth, the component (X) was removed from the obtained modified fiber cloth in the same manner as in Example 1. It was fixed in a state that it was difficult to release, had a good texture, exhibited a high skin care effect and a high moisture absorption in both the initial stage and after washing 20 times, and had excellent durability. On the other hand, in Comparative Example 3 in which the hydrophilization treatment was not performed, the obtained fiber fabric was significantly inferior in both skin care effect and hygroscopicity to Example 2. Table 4

(Example 3)

Nylon taffeta with a fabric mass of 100 g Zm ² was subjected to scouring, presetting and dyeing in a usual manner in a usual manner. Using this fiber fabric as a substrate, a modification treatment was performed. A fiber treatment solution having the composition shown in Table 5 was prepared and applied to the fiber cloth by the padding method. Drawing ratio was 5 0 mass ^_0/0. Thereafter, a wet heat treatment was performed for 5 minutes with steam at 105 ° C. and 98% RH to carry out polymerization. After the completion of the polymerization reaction, washing, drying, and finishing were performed. The resulting modified fiber fabric was evaluated. Table 5 Composition of fiber treatment solution (Example 3)

(Comparative Example 4)

Using the same nylon taffeta as in Example 3, scouring, pre-setting, dyeing, drying and finishing setting were sequentially performed in the usual manner to obtain a 100% nylon taffeta fabric. The obtained fiber cloth was evaluated. (Comparative Example 5)

A modified fiber fabric was obtained in the same manner as in Example 3 except that a fiber treatment solution having the composition shown in Table 6 was prepared. The resulting modified fiber fabric was evaluated. Table 6 Composition of fiber treatment solution (Comparative Example 5)

(Evaluation results of Example 3 and Comparative Examples 4 and 5)

P / C atomic ratio of the fiber fabrics obtained in Example 3 and Comparative Examples 4 and 5,

Table 7, Fig. 5 and Fig. 6 show the index and hygroscopicity test results, respectively.

In Example 3, in which the component (X) and the components (A) to (C) were polymerized and modified on the fiber cloth, as in Example 1, the obtained modified fiber cloth had the component (X) removed. It was fixed in a state that it was difficult to release, had a good texture, showed a high skin care effect and high moisture absorption on both sides after washing about 20 times, and had excellent durability . On the other hand, in Comparative Example 4 in which the hydrophilization treatment was not performed, the obtained fiber cloth was significantly inferior in skin care effect, hygroscopicity, and deviation as compared with Example 3. In Comparative Example 5 in which only the component (X) was polymerized and modified on the fiber cloth, as in Comparative Example 2, although the obtained fiber cloth had the component (X) introduced, Since it adhered only to the surface, the moisture absorption was insufficient. In addition, component (X) was desorbed, and the durability was insufficient. Table 7

(Example 4)

A knitted nylon tricot with a fabric weight of 120 g Zm ² was subjected to scouring, presetting, and dyeing in order by a conventional method. Using this fiber fabric as a base material, a modification process is performed.

The same fiber treatment liquid as in Example 3 was applied to the fiber cloth by a padding method. The aperture ratio is 80 mass. / ₀ . Next, after drying at 120 ° C for 5 minutes, a wet heat treatment of treating with steam at 115 ° C and 97% RH for 30 minutes was performed to carry out polymerization. After completion of the polymerization reaction, a finishing set was performed. The resulting modified fiber fabric was evaluated.

(Comparative Example 6)

Presetting, dyeing, drying and finishing setting were sequentially performed on the same nylon tricot knitted fabric as in Example 4 to obtain a 100% nylon tricot knitted fabric. The obtained fiber cloth was evaluated.

(Evaluation results of Example 4 and Comparative Example 6)

PZC atomic ratio of the fiber fabrics obtained in Example 4 and Comparative Example 6,

The numbers and results of the hygroscopicity test are shown in Table 8, Figure 7, and Figure 8, respectively.

In Example 4 in which the component (X) and the components (A) to (C) were polymerized and modified on the fiber cloth, the component (X) was removed from the obtained modified fiber cloth in the same manner as in Example 1. Established in a state that is difficult to remove, has a good texture, and smells both at the initial stage and after washing 20 times It showed high skin care effect and high hygroscopicity, and was excellent in durability. On the other hand, in Comparative Example 6 in which the hydrophilization treatment was not performed, the obtained fiber fabric was significantly inferior to Example 4 in skin care effect, hygroscopicity, and slippage. Table 8

(Sika 5)

Broad woven fabric mass 150 g / m ² (warp: Polyester 1 100%, weft yarn: 65% polyester and 35% of the spun yarn cotton) against, relaxing scan in a conventional manner, scouring, presetting, alkali Weight reduction and dyeing were performed sequentially. The fiber fabric was used as a substrate, and a modification treatment was performed.

A fiber treatment solution having the composition shown in Table 9 was prepared and applied to the fiber cloth by the padding method. Squeezing ratio was 70 mass ^_0/0. Thereafter, a wet heat treatment was performed for 5 minutes with steam at 110 ° C and 98% RH to carry out polymerization. After the polymerization reaction was completed, washing and finishing set were performed. The resulting modified fiber fabric was evaluated.

Table 9 Composition of fiber treatment liquid (Example 5)

Ingredients

(Parts by mass) Ingredient (X) 2-Metharylloyloxhetyl phosphorylcholine 5

And n-butyl methacrylate copolymer

Ingredient (A) 5

CH ₂ = CH— C00 (CH ₂ CH ₂ 0) ₂₃ 0C— CH = CH ₂ component (B) Acrylic acid 0.5 component (C) 0.3

Surfactant ET 135 (Noniona 0.15 dione system manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Polymerization initiator V50 (Wako Pure Chemical Industries, azo system) 0 5 Water 88. 9

(Comparative Example 7)

The same broad fabric as that in Example 5 was subjected to relaxation, scouring, presetting, alkali weight reduction processing, dyeing, and finishing set in the usual manner. The obtained fiber cloth was evaluated. (Comparative Example 8)

The same broad fabric as in Example 5 was subjected to relaxation, scouring, presetting, alkali weight reduction processing, and dyeing in the same manner as in Example 5. The fiber fabric was used as a substrate, and a modification treatment was performed.

A fiber treatment liquid having the composition shown in Table 10 was prepared and applied to the fiber cloth by the padding method. The drawing ratio was 70% by mass. Then, after finishing drying at 120 ° C for 3 minutes, a finishing set of heating at 170 ° C for 1 minute was performed. The obtained fiber cloth was evaluated. It should be noted that the polymerization reaction does not proceed only by performing the dry heat treatment after the application of the fiber treatment liquid. Table 10 Composition of fiber treatment solution (Comparative Example 8)

(Evaluation results of Example 5 and Comparative Examples 7 and 8)

PZC atomic ratio of the fiber fabrics obtained in Example 5 and Comparative Examples 7 and 8,

Table 11, Figure 9, and Figure 10 show the results of the 指数 index and the moisture absorption test.

In Example 5, in which the component (X) and the components (A) to (C) were polymerized and modified on the fiber cloth, as in Example 1, the component (X) was removed from the resulting modified fiber cloth. It was fixed in a state that it was difficult to release, had a good texture, exhibited a high skin care effect and a high moisture absorption in both the initial stage and after washing 20 times, and had excellent durability. On the other hand, in Comparative Example 7 in which the hydrophilization treatment was not performed, the obtained fiber cloth was significantly inferior to Example 5 in skin care effect, hygroscopicity, and deviation. In addition, although the solution containing the component (X) was brought into contact with the fiber cloth, only the dry heat treatment was performed, and in the comparative example 8 in which the polymerization was not performed, it was confirmed that the component (X) was introduced. However, after 20 washes, the atomic ratio of PZC was significantly reduced, and most components (X) were eliminated by washing. This is because component (X) remained as a monomer and adhered only to the fiber surface. In addition, since the component (X) was introduced only into the surface of the fiber, the initial hygroscopicity was significantly inferior to that of Example 5. In addition, the modified fiber fabric obtained a high skin care effect at the beginning, but after washing 20 times, the skin care effect was greatly reduced with the elimination of the component (X). Thus, the fiber fabric obtained in Comparative Example 8 was insufficient in hygroscopicity and durability.

From the above Examples and Comparative Examples, by polymerizing the component (X) and the components (A) to (C) on the fiber cloth, it is possible to fix the component (X) not only on the surface of the fiber but also inside the fiber. It has been found that a modified fiber fabric that is excellent in moisture absorption, durable, and has a high skin care effect can be obtained. In the above examples, only the case where 2-methacryloyloxetyl phosphorylcholine or a polymer thereof was used as the component (X) was described. It has been confirmed that similar results can be obtained by using cryloyloxetyl phosphorylcholine ゃ 2 -metacloyloxetylphosphorylcholine or a polymer thereof. In the above examples, the component (X) and the component

Although only the case where (A) to (C) are polymerized at the same time has been described, the present inventor has obtained the same result by polymerizing components (A) to (C) and then polymerizing component (X). Obtained Make sure that. Industrial applicability

According to the present invention employing a specific polymerization reaction, a low-irritation modification that is excellent in water absorption and moisture absorption, excellent in durability, and has a high skin care effect while ensuring a feeling such as flexibility and drape property. And a method for producing the same.

The modified fiber fabric of the present invention is particularly useful for direct and continuous contact with the skin, for example, underwear, clothes, lining of clothes, gloves, shoes, socks, sports clothing, bedding (sheets, covers, It can be suitably used for applications such as the futon) and towels. When used for these applications, it is suitable because it quickly absorbs sweat and the like to give the user an exhilarating sensation while ensuring a texture such as flexibility and drapability, and has little skin irritation. It is also possible to provide the user with skin care effects such as moisturizing the skin and promoting natural healing of rough skin.

The scope of the present invention is defined by the appended claims, and is not restricted by the body of the specification. Further, all modifications and changes belonging to the equivalent scope of the claims are within the scope of the present invention.

Claims

The scope of the claims

1. On a fiber cloth, it is a monomer containing a phosphorylcholine analogous group selected from 2- (meth) acryloyloxetylphosphorylcholine or 2_methacryloxyshethylphosphorylcholine and Z or a polymer thereof. Component (X), component (A) which is a bifunctional monomer represented by the following general formula (1), and any one of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and a phosphate group A modified fiber fabric obtained by polymerizing a component (B), which is a monomer containing, and a component (C), which is a monomer containing at least one aziridine group.

Z CH ₃ CH ₃ Z

CH ₂ = C-C00 (CH ₂ CH ₂ 0) _a (CH ₂ — CH0) x— R— (0CHCH ₂ ) _y (0CH ₂ CH2) b 00C— C: CH ₂

(However, in the equation (1), R is

-C _n H _2n - (where, n is an integer of 1-6.) Represents any of. Z represents a hydrogen atom or a methyl group. a and b represent a positive integer in which a + b is in the range of 0 to 50, and X and y represent 0 or a positive integer in which x + y is in the range of 0 to 30. A + b + x + y is 10 or more. )

2. The modified fiber fabric according to claim 1, wherein the component (X) and the components (A) to (C) are introduced into the surface and inside of the fiber.

3. The modified fiber fabric according to claim 1, wherein the component (X) and the components (A) to (C) are graft-polymerized on the fiber fabric.

4. On fiber fabric, 2- (meth) acryloyloxyshethyl phosphorylcholine Or by polymerizing a phosphorylcholine analog-containing monomer selected from 2-methacryloxyshethylphosphorylcholine and / or a component (X) which is a polymer thereof, wherein the component (X) is formed on the fiber surface and A modified fiber fabric characterized by being introduced inside.

5. The fiber fabric is made of 2- (meth) acryloyloxyshethylphosphorylcholine or a phosphorylcholine-analogous group-containing monomer selected from 2-methacryloxylshethylphosphorylcholine and / or a polymer thereof. A modified fiber fabric obtained by graft-polymerizing a component (X).

6.2-(Meth) ataliloyloxetyl phosphorylcholine or 2-metacloyloxetyl phosphorylcholine selected from phosphorylcholine analog-containing monomer and / or its component (X), Component (A), which is a bifunctional monomer represented by the general formula (1), is a monomer containing any one of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and a phosphate group. A fiber treatment solution comprising: component (B); and component (C), which is a monomer containing at least one aziridine group.

2 CH ₃ CH ₃ Z

CH ₂ = C— C00 (CH ₂ CH ₂ 0) _a (CH ₂ CH0) r R— (0CHCH ₂ ) _y (0CH ₂ CH ₂ ) _b 00C C = CH ₂

• "(1)

(However, in the equation (1), R is

C _n H _{2 n} — (where n represents an integer of 1 to 6). Z represents a hydrogen atom or a methyl group. a and b represent a positive integer in which a + b is in the range of 0 to 50, and X and y represent 0 or a positive integer in which x + y is in the range of 0 to 30. A + b + x + y is 10 or more. )

7. The fiber treatment solution according to claim 6, wherein the solvent contains water, Z or an aliphatic lower alcohol having 1 to 3 carbon atoms.

8. A liquid contacting step of bringing the fiber treatment liquid according to claim 6 into contact with a fiber cloth,

A polymerization step of polymerizing the component (X) and the components (A) to (C) on the fiber cloth.

9. The method for producing a modified fiber cloth according to claim 8, wherein in the polymerization step, the component (X) and the components (A) to (C) are graft-polymerized to the fiber cloth.

10. Component (A) which is a bifunctional monomer represented by the following general formula (1), a monomer containing any one of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and a phosphate group A first liquid contacting step in which a fiber treatment solution containing a component (B) as a body and a component (C) as a monomer containing at least one aziridine group is brought into contact with the fiber cloth; A first polymerization step of polymerizing (A) to (C);

A polymer containing the components (A) to (C) is polymerized with a phosphorylcholine-like group-containing monomer selected from 2- (meth) atalyloyloxyshetyl phosphorylcholine or 2-methacryloyloxyshetylphosphorylcholine and Z Or a second liquid contacting step of contacting a solution of the component (X), which is a polymer thereof,

A second polymerization step of polymerizing the component (X) on the fiber cloth. Z CHg CH ₃ Z

CH ₂ = C C00 (CH ₂ CH ₂ 0) _a (CH2—CH0) x R— (0CHCH ₂ ) _y (OCH ₂ CH ₂ ) _b 00C— C = CH ₂

(However, in the equation (1), R is

_C _n H _2n — (where n is an integer from 1 to 6). Z represents a hydrogen atom or a methyl group. a and b represent a positive integer in which a + b is in the range of 0 to 50, and X and y represent 0 or a positive integer in which x + y is in the range of 0 to 30. A + b + x + y is 10 or more. )

11. The modification according to claim 10, wherein the fiber treatment solution and the solution of the component (X) contain water and Z or an aliphatic lower alcohol having 1 to 3 carbon atoms as a solvent. A method for producing a fiber fabric.

12. In the first polymerization step, the components (A) to (C) are graft-polymerized on the fiber cloth, and in the second polymerization step, the component (X) is graft-polymerized on the fiber cloth. 11. The method for producing a modified fiber cloth according to claim 10, wherein: