WO2005026431A1

WO2005026431A1 - Fibrous structure

Info

Publication number: WO2005026431A1
Application number: PCT/JP2003/011540
Authority: WO
Inventors: Aya Haseyama; Atsushi Shinozaki; Hidenobu Honda; Koichi Saito
Original assignee: Toray Industries, Inc.
Priority date: 2003-09-10
Filing date: 2003-09-10
Publication date: 2005-03-24
Also published as: AU2003262037A1

Abstract

A fibrous structure having the long-lasting ability to remove formaldehyde and volatile organic compounds regarded as substances causative of sick building syndrome. The fibrous structure is characterized in that a composite oxide containing titanium and silicon and an aldehyde remover are adherent to the surface of fibers through a binder resin. The aldehyde remover may be one comprising a hydrazide compound or nitrogenous heterocyclic compound.

Description

Description Textile structure Technical field

TECHNICAL FIELD The present invention relates to a fibrous structure having durable deodorant performance against formaldehyde-volatile organic compound which is said to be a causative substance of sick house syndrome.

For more details, beddings such as cotton, cloth, mats, blankets, mattresses, dakimakura, bed mats, curtains, covers, etc. used for sofas, cushions, plushies, cushions, comforters, mattresses The present invention relates to a fiber structure that can be widely applied to textiles having a surface layer made of fibers, such as fabrics used for goodwill and slippers, carpets, carpets, mats, and automobile interior materials. Background art

In recent years, as people's standards of living have improved, their awareness of health has also increased, and the development of new deodorants and the practical application of deodorized textile products are being promoted one after another. However, deodorants that are effective against all kinds of odors have not yet been developed, and volatile organic compounds such as formaldehyde II, xylene, toluene, ethylbenzene, and styrene (hereinafter abbreviated as VOC) that are not produced in daily life. Deodorized textile products having an effective deodorizing function against water have not yet been reported. That is, since VOC such as xylene is an aromatic compound with low polarity, the deodorizing function for odorous substances having polar functional groups, which has been the target of ordinary deodorizing processing, is an effective deodorant for VOC. The odor effect could not be exerted. These odorous substances are used extensively in building materials, etc., and as a result, are contained a lot in the internal environment of new houses and new cars, and are said to be the causative substances of sick house syndrome. In recent years, it has become clear that various forms of health disorders can be caused by the inhalation of formaldehyde VOCs into the body by respiration. The appearance has been awaited. Therefore, an object of the present invention is to provide a fiber structure having durable deodorizing performance against formaldehyde VOC in view of the problems of the conventional deodorized processed fiber product. . Disclosure of the invention

The present invention employs the following means to achieve the above object. That is, the fiber structure of the present invention is characterized in that a composite oxide composed of titanium and silicon and an aldehyde deodorant adhere to the fiber surface via a binder resin. Things. BEST MODE FOR CARRYING OUT THE INVENTION

The composite oxide containing titanium and silicon used in the present invention is a composite oxide in which both titanium and silicon are contained in a compound, and mainly exhibits a function as a photocatalyst. Here, the photocatalytic function is a catalytic function for oxidatively decomposing organic substances by a strong oxidizing power excited by ultraviolet rays.

In general, a binary composite oxide composed of titanium and silicon is, for example, a solid as described in “Catalyst” Vol. 17, No. 3, page 72 (1975). It is known as an acid, exhibits remarkable acidity not found in the oxides of the constituent metals alone, and has a high surface area. That is, since titanium and silicon form a binary oxide and are complex oxides in which silicon is contained in the crystal lattice of titanium oxide, unique characteristics are exhibited.

Some of these composite oxides have a crystal structure called anatase type or rutile type.However, from the viewpoint of further improving the deodorizing function of the composite oxide, titanium oxide was analyzed by X-ray diffraction. (4) It is preferable to use an amorphous or near-amorphous microstructure that has a broad diffraction peak without the intrinsic peak of silicon oxide.

The molar ratio of titanium to silicon in the composite oxide is preferably in the range of 20 to 95 mol% and the silicon in the range of 5 to 80 mol%. The photocatalytic activity tends to weaken as the proportion of silicon increases, so determine the optimal proportion according to the purpose of use. Preferably.

It is also preferable that this composite oxide contains a metal element other than titanium and silicon. Preferable examples of other metal elements include tungsten, manganese, molybdenum, cerium, cobanoleto, niobium, eckenole, zinc, dinocononium, tin, tantanole, and lanthanum.

The composite oxide containing titanium and silicon can be produced, for example, by the method described in Japanese Patent Publication No. 5-515184.

As a preferable production method, a sulfuric acid aqueous solution of sulfuric acid titanyl is dropped into a mixed solution of aqueous ammonia and silica gel to form a precipitate. The precipitate is filtered, washed, dried, and then dried. To 650 ° C. According to this production method, it is possible to obtain an oxidatively decomposable catalyst which is superior in the oxidatively decomposable characteristics of organic substances and has a high deodorizing effect as compared with a generally known titanium oxide photocatalyst.

It is considered that the deodorizing reaction by such a composite oxide is performed through a process in which malodorous components are adsorbed by a catalyst and then undergoes oxidative decomposition by ultraviolet rays. Is preferably in the form of particles, particularly preferably in the form of porous particles. If the particle diameter is too large or the specific surface area is too small, the decomposition rate for organic substances tends to decrease. The average primary particle diameter of the composite oxide is preferably from 1 to 20 nm, and the specific surface area is preferably from 100 to 300 m from the viewpoint of efficiently adsorbing malodorous components.

Here, the specific surface area of the composite oxide is a value measured using a QUANT ASORBOS-8 device manufactured by QUANT ACHROME, and can be measured by the following method.

[Method for measuring specific surface area of composite oxide]

Measure using QUANTA SORB OS-8 manufactured by QUANTA CHROME under the following conditions.

Measurement conditions: DE T—one-point method, distribution method, TDC detection

Pretreatment conditions: N ₂ under 250 ° C X 15 minutes

The average primary particle diameter of the composite oxide may be measured by the following method.

[Method for measuring average primary particle diameter of composite oxide]

Magnification: 10 using a transmission electron microscope JEM-210 manufactured by JEOL Ltd. Measure by a factor of 10,000.

The amount of the composite oxide attached to the fiber structure is 0.01 to 10 weight per fiber. /. Is preferred. The adhesion amount is 0.01 weight. /. If the amount is less, the decomposition rate of the odorous components becomes slow and the deodorizing function becomes insufficient. 10 weight. /. If the amount is larger, there is a concern that the fiber fabric may be deteriorated by the oxidizing action of the composite oxide.

The aldehyde deodorant used in the present invention is a chemical substance that exhibits a deodorizing function for aldehydes, and among them, a deodorant containing a hydrazide compound or a nitrogen-containing heterocyclic compound is preferable. Used. These compound-based deodorants are preferable because they cause a chemical reaction with and adsorb aldehydes such as formaldehyde, so that re-emission of the aldehyde can be prevented.

Examples of the hydrazide compound include adipic acid dihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, terephthalic acid dihydrazide and the like. Further, as the nitrogen-containing heterocyclic compound, azoles and azines are preferable. Specifically, 3-methyl-5-pyrazolone, pyrazole, 6-methyl-8-hydroxytriazolopyridazine, 1, 2,4-triazole and the like. Among them, adipic dihydrazide is particularly preferred.

In the present invention, it is important to simultaneously provide a compound having a photocatalytic function, which is a composite oxide of titanium and silicon, and an aldehyde deodorant containing a hydrazide compound or a nitrogen-containing heterocyclic compound. When these two deodorants are combined and adhered, the deodorant performance against VOC substances such as toluene is dramatically improved. This is because the interaction between the π electrons present in the molecule of the hydrazide compound and the nitrogen-containing organic heterocyclic compound and the π electrons present in the aromatic ring of the VOC attracts the VOC substance to the surface of the fiber structure. This is due to the fact that it is oxidatively decomposed and rendered harmless by the composite oxide present on the fiber surface.

From this deodorizing mechanism, the amount of the aldehyde deodorant attached is preferably 0.5 to 100% by weight based on the amount of the complex oxide containing titanium and silicon. 100 weight. /. If more aldehyde deodorant is attached, VOC is adsorbed to the aldehyde deodorant and is difficult to move to the composite oxide side, so it is difficult for oxidative decomposition to proceed, and 0.5 weight. If the _ratio is less than 0/0, the number of VOCs captured by the fiber surface will decrease dramatically, This is because the OC decomposition function cannot be sufficiently exhibited.

In the present invention, the binder resin used for adhering the composite oxide and the aldehyde deodorant to the fiber surface has good adhesion to the fiber surface and is subject to decomposition by the photocatalytic action of the composite oxide. Any resin that is difficult can be used. For example, polyurethane resin, silicone resin, fluororesin, acrylic resin, polyester resin, melamine resin, etc. are used.In particular, the components of polyurethane resin, silicone resin, acryl resin, and polyester resin are used. Those containing one or more are preferably used. Among the polyurethane resins, a water-soluble polyurethane resin is preferable because of less burden on the environment. Further, as a crosslinking agent in that case, an isocyanate or a silane coupling agent is preferably used.

If the fibrous structure to be processed to adhere the composite oxide and the aldehyde deodorant is short-fiber cotton, the silicone is less sticky because of the post-processability of cards and the like. Resins and / or polyester resins are preferred.

The amount of the binder resin attached is 0.01 to 5 wt. / _0, preferably 0.1 to 1 weight. / ₀ is more preferred. 0.01 weight of resin attached

If less than 5%, the binder effect of adhering the composite oxide and the aldehyde deodorant is weakened, and the weight is 5 wt. If the ratio is more than ₀ , the texture of the fiber structure becomes coarse and hard, and the practicality is poor.

The fiber structure referred to in the present invention is a fiber product composed of fibers, and may have any structure and shape. For example, fabrics such as woven fabric, knitted fabric, non-woven fabric, and suede-like artificial leather, band-like materials, string-like materials, cotton-like materials, net-like materials, or intermediate products such as composite materials in which the surface layer is composed of fibers. Textiles, or final textiles such as pets, curtains, and moquettes. Among them, woven fabric, knitted fabric, non-woven fabric and cotton are preferred.

The fibers constituting the fibrous structure may be fibers having any cross-sectional shape. When the type of the fiber is a synthetic fiber, a semi-synthetic fiber, or a regenerated fiber, the cross-section of the fiber may be an ordinary round cross-section, but from hollow, H-type, X-type, W-type, Y-type, and star-type. It is preferable that the deformed cross section has at least one selected ^ shape. The fibers having such a cross-sectional shape can be obtained by changing the shape of the die at the time of spinning, or It can be easily manufactured by a method in which a certain kind of polymer is composite-spun and divided and split in a later step, or one is eluted and removed.

Various fibers such as synthetic fibers and natural fibers can be used without particular limitation. Examples of synthetic fibers include polyester fibers, nylon 6 fibers, polyamide fibers such as nylon 66 fibers, polyacryl fibers, polyacrylonitrile fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, and polypropylene arrowheads. Fiber, urethane fiber, polylactic acid fiber, etc .; semi-synthetic fiber, diacetate fiber, triacetate fiber, etc .; and regenerated fiber, rayon fiber, cuvula fiber, Tencel Examples of the natural fiber include wool, silk, cotton, hemp, and the like, but are not limited thereto. In addition, two or more of these fibers may be used as a mixture at an arbitrary ratio, or may be used in combination. Among them, polyester fibers are preferably used in terms of washing durability and the like.

As such polyester fibers, polyethylene terephthalate fibers, polypropylene terephthalate fibers, polybutylene terephthalate fibers, and polyhexamethylene terephthalate fibers are preferred. Further, fibers obtained by copolymerizing other components are also preferable. As the other components, isophthalic acid, 5-sodium sulfoisophthalic acid, methoxypolyoxyethylene dalichol, and the like are preferably used.

The deodorizing function according to the present invention has a weight of 50% of the total fibers constituting the fiber structure. It is preferable that polyester fibers have a ratio of / ₀ or more, because particularly excellent effects are exhibited. Polyester fibers have high chemical resistance and are less susceptible to photocatalysis than other fibers.

Further, the polyester fiber constituting the fiber structure of the present invention preferably contains inert titanium oxide in the fiber. This inactive titanium oxide is preferably inactive at a level that is not excited by light of a specific wavelength, particularly ultraviolet light, and is used as a matting agent in the production of ordinary polyester fibers. Titanium oxide is preferably used. The addition of the inert titanium oxide increases the inorganicity of the polyester-based fiber, thereby reducing the adverse effect of the redox effect caused by the composite oxide attached to the fiber surface on the polyester-based fiber. be able to'.

Such inert titanium oxide may be added in the polyester polymerization step for spinning polyester fibers. The average particle size of the inert titanium oxide is preferably in the range of 0.1 to 0.7 μτη, and more preferably in the range of 0.2 to 0.4 μm, from the viewpoints of spinning properties and thread properties.

The amount of the inert titanium oxide is preferably 0.3 to 5.0% by weight, more preferably 0.5 to 4.0% by weight, based on the weight of the fiber. 0.3 weight. /. If it is less than 1, the polyester fiber is easily decomposed by the attached composite oxide, and the photocatalytic function and the durability of the intrinsic physical properties of the fiber tend to be poor. On the other hand, if it exceeds 5.0% by weight, the spinning properties and yarn properties tend to be insufficient.

In addition, polyester fibers into which carbon black has been kneaded are preferably used for applications requiring light-shielding properties, such as strength.

It is preferable that the fiber constituting the fiber structure of the present invention contains a flame retardant inside the fiber and / or adheres to the fiber surface. The flame retardant effect of the flame retardant does not depend much on the location of the flame retardant in the fiber, and is greatly affected by the weight ratio of the flame retardant to the fiber weight. As a method for containing or adhering a flame retardant to fibers, a method of adding a flame retardant to a dyeing solution and performing an adhering treatment at the same time as dyeing, a method of impregnating and impregnating a flame retardant-containing solution, or There is a method in which a synthetic fiber is contained in the fiber by copolymerization or kneading during production.

Flame retardant is 1 to 30 weight based on fiber weight. /. It is preferred that it be included in the proportion of 1 weight. If it is less than / _0, it is difficult to obtain sufficient flame retardancy, and if it exceeds 30% by weight, the texture tends to be coarse and hard.

As such a flame retardant, a flame retardant containing at least one of boron, phosphorus, nitrogen, antimony, and halogen is preferable, and particularly, a phosphoric ester flame retardant and a bromine flame retardant are preferably used. Can be

Flame retardants applied to polyester fibers include phosphoric acid esters, aromatic phosphates, carboxyphosphinic acid and its cyclic anhydrides, cyclic phosphinic acid derivatives, phosphonic acid derivatives, phosphoryl compounds, and halogenated aliphatics. Phosphorus compound flame retardants such as phosphate esters, halogenated diols, halogenated glycidyl ethers, Halogen flame retardants such as halogenated cycloalkane, brominated bisphenol A and brominated bisphenol S, metal compounds such as antimony oxide, boron compounds and silicon compounds are preferably used. These flame retardants may be incorporated into the fiber by a method of copolymerizing in polyester or kneading in a polyester polymer, or may be exhausted into fibers by post-processing into polyester fabric. Alternatively, it may be attached by impregnation.

Specific examples of the flame retardant include 2-carboxyethyl-methyl-phosphinic acid, its cyclic anhydride, tris (2,3-dibromopropyl) phosphate, and resorcinol'bis (diphenylphospho). Fet) and a mixture of resonoresinol 'bis (dixylenyl phosphate) and triphenyl phosphate, hexaboxime cyclododecan, tetrabrombisphenenole A, 2, 2-bis (4-hydroxyethoxyethoxy) — 3, 5-dibromopheny ^^)

As a flame retardant applied to acryl fibers, a butyl chloride monomer is preferable. Further, a flame-retardant acrylic fiber produced from a polymer obtained by copolymerizing a vinyl chloride monomer with acrylonitrile may be used.

Preferred flame retardants applied to cotton fibers include tetrakishydroxymethylphosphonium salt and N-methyloldimethylphosphonopropionamide.

In order to further improve the flame retardant effect, it is preferable to attach the composite flame retardant and the aldehyde deodorant to the fiber surface simultaneously with the treatment for attaching the flame retardant.

Next, an example in the case where the fiber structure of the present invention is manufactured by processing a fabric will be described.

First, an aldehyde deodorant is dissolved in water, and then a composite oxide and a binder resin are added and mixed to obtain an aqueous dispersion. At this time, if necessary, a flame retardant, a negative ion generator, a water repellent, an antibacterial agent, a form stabilizing agent, a moisture absorbent, a heat insulating agent, and a water absorbent may be further added. The obtained aqueous dispersion is used as a working liquid.

Then, after impregnating the fabric with the working fluid, the fabric is squeezed with a mangle roll and dried and cured. Alternatively, a viscosity adjusting agent is added to the working fluid to adjust the viscosity to a desired value. After applying it to the fabric surface by means of a coater, gravure coater, printing, spraying, etc., fix it at a temperature of 200 ° C or less. The complex oxide and aldehyde deodorant are attached to the fiber surface by the following method.

The processed fabric thus obtained has a deodorizing performance which has never existed before, and also has durability.

This processed fabric includes beddings such as comforters, mattresses, mats, blankets, sleepers, dakimakura, bed mats, sofas, cushions, cushions, plush toys, curtains, carpets, mats and covers. It can be applied to interiors such as automobiles, goodwill and slippers, and interior materials for vehicles such as car seats, and can effectively reduce formaldehyde VOCs present in the environment. Wear.

In addition, in order to apply to interiors used in public facilities such as hospitals and hotels, it is preferable to apply a flame retardant to the fiber surface to obtain a processed fabric having flame retardancy. Hereinafter, the present invention will be described in more detail with reference to Examples.

The properties of the fiber structures obtained in the following Examples and Comparative Examples were measured and evaluated by the following methods.

(Measurement of formaldehyde deodorant using a detector tube)

Pour 3 g of the sample into a 500 ml container, add an aqueous solution of formaldehyde so that the initial concentration is 4 ppm, seal the mixture, allow it to stand for 30 minutes, and use a gas detector tube to measure the residual formaldehyde concentration. It was measured. From this residual concentration and the initial concentration, the formaldehyde deodorization rate (%) was calculated according to the following equation. When the sample was cotton, the sample was put in a gauze bag in which two squares each having a side of 10 cm were sewn and evaluated for deodorization.

Deodorization rate (%) = {1-(residual concentration) Z (initial concentration)} X 100

(Measurement of xylene deodorant by detector tube)

The deodorizing property of xylene was measured as a representative of VOC. Prepare a container containing the sample in the same manner as in the measurement of formaldehyde deodorization described above, put xylene in this container so that the initial concentration is 40 ppm, and seal it, and leave it for 2 hours. And After that, the residual xylene concentration was measured with a gas detector tube. From this residual concentration and the initial concentration, the xylene deodorization rate (%) was calculated according to the above formula for calculating the deodorization rate.

(Measurement of formaldehyde deodorant and xylene deodorant after 5 washes)

Using a self-reversing spiral electric washing machine VH-340 (manufactured by Toshiba Corporation), under the conditions of a commercially available detergent concentration of 0.2%, a temperature of 40 ± 2 ° C, and a bath ratio of 1:50. Washing was performed with strong inversion for 5 minutes, then draining, and rinsing for 2 minutes while overflowing was repeated twice, and this was defined as one washing.

After the washing was repeated 5 times, the fibrous structure was used as a sample, and the formaldehyde deodorizing property and the xylene deodorizing property were measured by the same method as described above.

(Evaluation of flame retardancy)

When the sample was a woven fabric, the flame retardancy was evaluated according to the JIS L 1091 textile product combustion performance test method. Tests of A-1 and D methods were conducted, and pass / fail judgment was made based on the Fire Service Law (a) label standards.

In the case of a sample, the flame retardancy was evaluated by the 45 ° mesenamine basket method.

(Measurement of water repellency)

JISL—1092 The water repellency was evaluated by the shower method. The higher the number, the better the water repellency.

(Measurement and evaluation of antibacterial properties)

Based on the method described in JIS L-1990, the bacteriostatic activity of Staphylococcus aureus was measured by a quantitative test method. The higher the number, the better the antibacterial performance. The bacteriostatic activity value was 2.2 or more, and the antibacterial performance was judged to be acceptable.

[Example 1]

0.35 weight of inert titanium oxide having an average particle diameter of 0.3 μm. /. Containing polyethylene Satin woven fabric of terephthalate multifilament yarn (83 dtex) with a basis weight of 200 g Zm ² is refined, dried and intermediately set under normal processing conditions, and then a brominated flame retardant. 30? — 1 Improve ₈ "(R) (manufactured by Daikyo Chemical Co., Ltd.) and stain with a disperse dye to obtain a flame retardant fabric with a 12% owf of flame retardant. .

As a composite oxide containing titanium and silicon, "TR-T2" (R) (a water-dispersed chemical solution having a solid content of 20%) manufactured by Daikyo Chemical Co., Ltd. was used. This is an aqueous dispersion in which a composite oxide of titanium and silicon having an average primary particle diameter of 7 ηm and an average specific surface area of 150 m ² Zg is dispersed in water at a solid concentration of 20%. The composite oxide is dispersed in the form of particles having an average particle diameter of 0.3 μm.

Adipic dihydrazide was used as the aldehyde deodorant.

As a binder resin, a polyurethane resin “Hydran AP X—101 H” (R) (solid content: 60%) manufactured by Dainippon Ink and Chemicals, Inc., and an isocyanate crosslinking agent “CR— 60 N "(R) (solid content: 100%) manufactured by Dainippon Ink and Chemicals, Incorporated.

These components and the following phosphoric ester-based flame retardant were prepared in the following composition to prepare an aqueous dispersion of a processing agent.

(Composition of processing fluid)

Composite oxide of titanium and silicon: "TR-T2" (R) (solid content 20%) 0.3% by weight, manufactured by Daikyo Chemical Co., Ltd.

Aldehyde deodorant: Adipic dihydrazide 0.2% by weight

Polyurethane resin: "Hydran AP X—101 H" (R) (solid content 60

%) 0.2% by weight manufactured by Dainippon Ink and Chemicals, Inc.

Iso-Cross-linking agent: "CR-600N" (R) (solid content: 100%) 0.06% by weight, manufactured by Dainippon Ink and Chemicals, Inc. Phosphate flame retardant: "Bigol GPE—5 1 5" (R) (solids 60

%) 0.5% by weight manufactured by Daikyo Chemical Co., Ltd.

Water 9 8. 7 9 4% by weight The flame-retardant fabric is immersed in this processing solution, picked up with a mangle roll at 80% by weight, squeezed at 130 ° C for 2 minutes, and then heat-treated at 170 ° C for 1 minute. A woven fabric to which a titanium-silicon composite oxide and an aldehyde deodorant were attached was manufactured. The deodorizing properties of the processed fabric were evaluated, and the results are shown in Table 1. In addition, the flame retardancy of this processed fabric was at an acceptable level.

[Example 2]

Polyethylene terephthalate multifilament yarn (83 dtex) containing 0.35% by weight of inert titanium oxide with an average particle diameter of 0.3 μm, satin fabric with a basis weight of 200 g Zm ² was processed under normal processing conditions. The fabric was refined, dried, intermediately set, and dyed with a disperse dye to produce a beige dyed fabric.

As the composite oxide of titanium and silicon and the aldehyde deodorant, the same components as those used in Example 1 were used. In addition, as a binder resin, an acrylic resin "Light Epoch T23-M" (R) (solid content: 20%) manufactured by Kyoeisha Chemical Co., Ltd. was used.

These components were mixed with the following composition to prepare an aqueous dispersion of a processing agent.

(Composition of processing fluid)

Composite oxide of titanium and silicon: "TR-T2" (R) (solid content: 20%) 0.3 weight, manufactured by Daikyo Chemical Co., Ltd. /.

Aldehyde deodorant: 0.2 weight of adipic dihydrazide. /.

Acrylic resin "Light Epoch T 23-M" (R) (solid content 20%) Kyoeisha Chemical Co., Ltd. 0.2% by weight

99.3 weight of water. /. The dyed fabric is immersed in this processing solution, squeezed with a mangle roll at 80% by weight, dried at 130 ° C for 2 minutes, and then heat-treated at 170 ° C for 1 minute. A woven fabric to which a composite oxide of iron and silicon and an aldehyde deodorant were attached was manufactured. The deodorant properties of the processed fabric were evaluated, and the results are shown in Table 1.

[Example 3] Polyester fibers having a round cross section of single yarn fineness of 6.67 dte X were produced by melt spinning in a conventional manner. These were bundled into 556,000 dtex tows, which were mechanically crimped by a crimper to form crimped tows.

As the composite oxide containing titanium and silicon and the aldehyde deodorant, the same components as those used in Example 1 were used. As the binder resin, a silicone resin "BY22-826" (R) (solid content: 45%) manufactured by Toray Dow Corning Silicone Co., Ltd. was used. These components were blended with the following composition to prepare an aqueous dispersion of a processing agent.

(Composition of processing fluid)

Composite oxide of titanium and silicon: "TR-T2" (R) (solid content 20%) 10% by weight, manufactured by Daikyo Chemical Co., Ltd.

Aldehyde deodorant: 2% by weight of adipic dihydrazide

Silicone resin "BY22-8226" (R) (solid content 45%) 10% by weight manufactured by Toray Dow Corning Silicone Co., Ltd.

Water 78% by weight Sprayed onto the crimped tow, 2% by weight of composite oxide of titanium and silicon. The working fluid was applied so as to be / _0, and dried with a continuous dryer set at 150 ° C for 10 minutes. After cutting this processed toe so that the single fiber length is 51 mm, it is set on a card machine, and a wadding-like filling with a titanium-silicon composite oxide and an aldehyde deodorant attached to the fiber surface. Manufactured cotton for use. The deodorizing properties of the cotton were evaluated, and the results are shown in Table 1.

[Example 4]

The island component was made of polyethylene terephthalate and the sea component was made of polystyrene.A two-component sea-island composite fiber with an island sea component ratio of 80/20 and 16 islands was produced by melt spinning. It was stretched 5 times, crimped, and cut to give a raw cotton of sea-island composite fiber with an island fineness of 0.2 dtex and an elongation rate of ultrafine island fiber of 115%. After using this raw cotton to make a fiber laminated web with carding and cross wrapper, A needle punch of 2000 pieces / cm ² was performed to produce a felt ground made of short fibers with a basis weight of 400 gZm ² . The thus obtained fiber ground is glued in hot water in which polyvinyl alcohol is dissolved, dried, then immersed in trichlorne and squeezed with a mandal to dissolve and remove sea components. Then, 29% of polyurethane based on the weight of felt was applied by wet coagulation. Thereafter, it brushed processing sliced, stained with disperse dye, to prepare a thick 0. 6 0 mm, basis weight 1 3 5 g / m ² artificial leather.

The same components as used in Example 1 were used as the composite oxide containing titanium and silicon and the aldehyde deodorant, and the same components as those used in Example 2 were used as the binder resin. These components were mixed with the following composition to prepare an aqueous dispersion of a processing agent.

(Composition of processing fluid)

Composite oxide of titanium and silicon: "TR-T2" (R) (solid content: 20%) 1.0 weight, manufactured by Daikyo Chemical Co., Ltd. /.

Aldehyde deodorant: Adipic acid dihydrazide 1.0% by weight Acrylic resin "Light Epoch T23-M" (R) (solid content 20%) Kyoeisha Chemical Co., Ltd. 1.0% by weight water 9 7.0% by weight The above-mentioned suede-like artificial leather is immersed in this processing liquid, and picked up with a mangle roll. /. And dried at 100 ° C for 2 minutes to obtain artificial leather having a composite oxide of titanium and silicon and an aldehyde deodorant adhered to the fiber surface.

Subsequently, this artificial leather was immersed in a water-repellent solution having the following composition, picked up with a mangle roll at 80% by weight, dried at 100 ° C. for 2 minutes to obtain a water-repellent treated artificial leather.

(Composition of water-repellent processing liquid)

Water repellent: "E C—400” (R) (solid content: 20%) manufactured by Keishin Kasei Co., Ltd.

1.0% by weight Melamine resin "Sumitec Resin M3" (R) (solid content: 80%) 0.2 weight, manufactured by Sumitomo Chemical Co., Ltd. /. Crosslinking agent "Sumitex Axelareiter AC X (solid content: 35%) manufactured by Sumitomo Chemical Co., Ltd. 0.04% by weight Water 8.76% by weight The deodorant property of the obtained artificial leather was evaluated. The results showed that the deodorant was good even after the water repellency treatment as shown in Table 1. The water repellency of the processed artificial leather was as good as grade 4.

[Example 5]

The total fineness 1 1 7 0 dtex, 8 1 filament Y-shaped cross-section nylon 6 Maruchifi Lament crimped yarn of TOUGH bets based fabric under normal conditions, and tough preparative pressurizing E fabric having a basis weight of 4 5 0 g / m ² Then, it was dyed according to a conventional method and backed to prepare a carpet. The same components as used in Example 1 were used as the composite oxide containing titanium and silicon. 3-Methyl-5-pyrazolone was used as the aldehyde deodorant. As the binder resin, a silicone resin “KT710” (R) (solid content: 40%) manufactured by Kyoeisha Chemical Co., Ltd. was used.

These components and the following antibacterial agent were prepared in the following composition to prepare an aqueous dispersion of a processing agent.

(Composition of processing fluid)

Composite oxide of titanium and silicon: "TR-T 2" (R) (solid content 20%, manufactured by Daikyo Chemical Co., Ltd.) 5% by weight

Aldehyde deodorant: 7 weight of 3-methyl-5-pyrazolone. / ₀ Silicone resin "KT70 14" (R) (solid content 40%) manufactured by Kyoeisha Chemical Co., Ltd.

5% by weight

Antibacterial agent: 1% by weight of 2-pyridylthiol-1-oxide zinc. / ₀ water 82% by weight Spraying the above-mentioned working fluid on the tuft surface of the pet by a spray so that the attached amount of the composite oxide of titanium and silicon becomes 5% by weight. ° C Drying was continued for 10 minutes using a continuous dryer to produce a carpet having a composite oxide of titanium and silicon, an aldehyde deodorant, and an antibacterial agent adhered to the fiber surface. This cartridge was evaluated for deodorizing properties, and the results are shown in Table 1. In addition, the antibacterial property of this tuft was at an acceptable level of 6.0 or more.

[Example 6]

Polyester step (2.2 dte XX 51 mm) Use 100% spun yarn (twisted yarn (cheese dyed)) for pile yarn and polyester stable (2.2 dtex X 51 mm) ) Weave using a blended yarn (cheese dyed) consisting of 65% and 35% rayon staple (2.2 dtex X 51 mm) for the ground yarn, brushing under normal conditions, pile length A moquette fabric having a thickness of ^2.5 mm and a basis weight of 5500 gZm ² was prepared and subjected to a backing treatment according to a conventional method to produce a moquette. The same components as those used in Example 1 were used as the complex oxide containing titanium and silicon and the aldehyde deodorant, and the same components as those used in Example 2 were used as the binder resin. . These components were mixed with the following composition to prepare an aqueous dispersion of a processing agent.

(Composition of processing fluid)

Composite oxide of titanium and silicon: "TR-T 2" (R) (solid content 20%) 1.0% by weight, manufactured by Daikyo Chemical Co., Ltd.

Aldehyde deodorant: 0.1% by weight of adipic dihydrazide

Acrylic resin "Light Epoch T23-M" (R) (solid content 20%) Kyoeisha Chemical Co., Ltd. 1.0% by weight

Water 97.9% by weight The moquette is immersed in this processing fluid and picked up by a mangle roll. / ₀ squeezed in, after drying for 2 minutes at 1 3 0 ° C, then heat-treated for 1 minute in 1 5 0 ° C, the fiber sheet surface, adhesion composite oxide and aldehyde deodorant of titanium and Kei-containing It was a moquette. The deodorizing properties of this processed moquette were evaluated, and the results are shown in Table 1.

[Example 7] The flame retardant fabric prepared in Example 1 was immersed in the working fluid used in Example 2 and picked up with a mangle roll. /. After drying at 130 ° C for 2 minutes, heat-treat at 170 ° C for 1 minute to remove the woven fabric with the composite oxide of titanium and silicon and an aldehyde deodorant attached to the fiber surface. Manufactured. The deodorizing properties of the processed fabric were evaluated, and the results are shown in Table 1. In addition, although the flame retardant was added to the processed fabric at the time of dyeing, the flame retardancy was rejected because the flame retardant was not included in the processing agent containing the composite oxide and the like.

[Comparative Example 1]

A fluid was prepared by removing the aldehyde deodorant component from the formulation of the working fluid of Example 1. The flame retardant woven fabric prepared in Example 1 was immersed in this processing liquid, and processed in the same manner as in Example 1 to produce a woven fabric having a composite oxide of titanium and silicon adhered to the fiber surface. This fabric was evaluated for deodorant properties, and the results are shown in Table 1. The flammability of this fabric was acceptable.

[Comparative Example 2]

A liquid was prepared by removing the composite oxide of titanium and silicon from the formulation of the processing liquid of Example 1. The flame retardant woven fabric prepared in Example 1 was immersed in this processing liquid, and treated in the same manner as in Example 1 to produce a woven fabric having an aldehyde deodorant adhered to the fiber surface. This fabric was evaluated for its deodorant properties, and the results are shown in Table 1. The flammability of this fabric was acceptable.

[Comparative Example 3]

From the formulation of the working fluid of Example 1, a solution was prepared in which the titanium-silicon composite oxide and the aldehyde deodorant were removed, and the flame retardant fabric prepared in Example 1 was immersed in this working fluid. Processing was performed in the same manner as in Example 1. This fabric was evaluated for deodorizing properties, and the results are shown in Table 1. The flammability of this woven fabric was acceptable.

[Comparative Example 4]

The deodorant properties of the flame-retardant woven fabric produced in Example 1 were evaluated without being treated with a working fluid, and the results are shown in Table 1.

[Comparative Example 5] The crimped tow prepared in Example 3 was cut to a single fiber length of 51 mm without being treated with a processing fluid, and then cut with a card machine to prepare a filling for filling in a wadding shape. . The deodorizing properties of the cotton were evaluated, and the results are shown in Table 1. '[Comparative Example 6]

The artificial leather produced in Example 4 was evaluated for its deodorant properties without being treated with a working fluid, and the results are shown in Table 1. The water repellency of this artificial leather was first class.

[Comparative Example 7]

With respect to the force and the softness prepared in Example 5, the deodorizing properties without treatment with the working fluid were evaluated, and the results are shown in Table 1. Also, since no machining fluid treatment was applied to this tough surface, the antibacterial property of this surface was 0.3, which was a reject level.

[Comparative Example 8]

The deodorant properties of the moquette prepared in Example 6 were evaluated without treatment with a machining fluid, and the results are shown in Table 1.

table

(*) Binder resin adhesion when applying complex oxide and aldehyde deodorant

As is clear from Table 1, the fibrous structures such as the flame retardant fabrics treated with the processing agents according to Examples 1 to 7 have excellent deodorization against formaldehyde and xylene which is a kind of VOC. It showed an effect, which persisted after washing. In particular, the flame retardant fabric treated with the processing agent according to Example 1 had both deodorant performance and flame retardancy.

On the other hand, as is clear from Comparative Examples 1 and 2, a sufficient deodorizing effect could not be obtained by attaching only one of the composite oxide and the aldehyde deodorant. In Comparative Examples 3 to 8 containing no deodorant, there was almost no deodorizing effect. Industrial applicability

The processing agent treatment according to the present invention can be widely applied to fibrous structures composed of fibers, such as semi-finished products such as fabrics, nonwoven fabrics and cotton, and end products such as moquettes and carpets. it can. Therefore, the fiber structure (fabric, non-woven fabric, cotton, etc.) according to the present invention includes sofas, cushions, stuffed animals, cushions, comforters, mattresses, mats, plankets, shells, dakimakura, bed mats, etc. Bedding, curtains, rugs, carpets, mats, covers, goodwill, slippers. It is useful as a material used for interior materials such as sheet materials and vehicle interior materials such as car seats, and can impart excellent deodorizing performance and the like to these materials. In addition, a fibrous structure having flame retardancy and deodorant performance can be obtained by using it together with a flame retardant, which is particularly useful for interiors in public facilities.

Claims

O 2005/026431 Scope of request

1. A fibrous structure characterized by being adhered to the fiber surface via a composite oxide containing titanium and silicon, an aldehyde deodorant, and a binder resin.

2. The fiber structure according to claim 1, wherein the composite oxide is in the form of particles having an average primary particle diameter of 1 to 20 nm.

3. composite oxide, 1 0 0~ 3 0 0 m and having a specific surface area of ² Z g, a fiber structure according to claim 1 or 2.

4. The attached amount of the composite oxide is 0.01 to 10 weight per fiber. /. The fibrous structure according to any one of claims 1 to 3, wherein

5. The fiber structure according to claim 1, wherein the aldehyde deodorant is a hydrazide-based compound or a nitrogen-containing heterocyclic compound.

6. The adhesion amount of aldehyde deodorant is 0.5 ~

The fiber structure according to any one of claims 1 to 5, which is 100% by weight.

7. The fiber structure according to any one of claims 1 to 6, wherein the shape of the fiber structure is one of a woven fabric, a knitted fabric, a nonwoven fabric, and a cotton.

8. The fibrous structure according to any one of claims 1 to 7, wherein 50% by weight or more of the fibers constituting the fibrous structure are polyester fibers.

9. The fiber structure according to claim 8, wherein the polyester fiber is a fiber containing 0.3 to 5.0% by weight of inert titanium oxide.

10. The fibrous structure according to any one of claims 1 to 9, wherein the fibrous structure is made of a fiber having a flame retardant inside and / or at the surface of the fiber.

1 1. Flame retardant is 1 to 30 weight based on fiber weight. The fibrous structure according to claim 10, wherein the fibrous structure is contained at a ratio of / ₀ .

12. The fibrous structure according to claim 10, wherein the flame retardant is a phosphate ester flame retardant or a bromine flame retardant.

13.The fiber according to any one of claims 1 to 12, wherein the binder resin contains at least one of a polyurethane resin, a silicone resin, an acrylic resin, and a polyester resin. Structure.