JPS6059171A - Surface roughened fiber structure and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fibrous structure made of roughened fibers and a method for producing the same, and particularly to f? The invention relates to a fiber structure with a new texture and a new function.

Various techniques are being studied to increase the depth of color in various dyed textiles, to improve the texture of cloth, or to add functionality. No technology has been established that simultaneously satisfies the characteristics or allows new effects to coexist without degrading performance, and such technology has been long-awaited.

Although natural fibers have characteristics such as hygroscopicity, they have poor dimensional and morphological stability, and the color development of dyed products is inferior compared to the vividness of natural flowers and insects. In addition, various organic synthetic fibers, especially melt-spun synthetic fibers, have a smooth fiber surface that gives them a unique waxy feel, a specular luster, poor color development in dyed products, and easy generation of static electricity.
It has been recognized that the disadvantage is that the texture is one step less than that of natural products.

Many of these imperfections are caused by the surface of the fiber, and as a means of modifying the fiber while preserving its basic properties, this can be achieved by surface roughening modification using fine particles and low-temperature deosma irradiation technology. That is.

Normally, roughening the fiber surface is thought to be a means of modifying the gloss or changing the texture, and fine particles such as titanium oxide are added to eliminate the luster, but this method only eliminates the luster. It is well known that color development deteriorates when This color development, deepness and sharpness of the wrinkled color are necessary conditions for any field of use of fibers.

In particular, polyester-based synthetic fibers are the most widely used due to their excellent functionality, but there are problems that need to be solved in terms of color development as mentioned above. This was especially requested.

Various techniques have been made public to solve the above problems.

The inventors of the present invention have previously published in Japanese Patent Application Laid-Open No. 107512/1983 regarding a technique for alkali-etching polyester fibers containing inorganic fine particles to form specific irregularities on the fiber surface, thereby obtaining a color miscoloring effect due to the rough rough surface. Proposed.

In addition, senior researchers have also developed a technique in which organic synthetic fibers are irradiated with glow discharge plasma to form specific irregularities on the fiber surface, and these irregularities produce a darkening effect.
It has been published as No. 99400.

The image quality is % that could not be achieved with conventional polyester fibers.
Although we are proud of the technology that can give a deep coloring effect, it is difficult to obtain a glossy dark color effect due to the decrease in gloss, and it is not suitable for use with composites of other materials such as blended fabrics and blended fibers. There were problems such as the narrow width.

The latter is the basis of the present invention in terms of manufacturing means, but it is related to a technique of plasma irradiation to ordinary synthetic fibers, that is, synthetic fibers that do not contain fine particles on the surface, and in the obtained synthetic fibers. Although the coloring property has been improved to some extent, it is still not satisfactory, and requires a long processing time, which does not increase the processing speed and causes cost problems. There are known methods to improve the color deepening effect by coating the surface with molecules or silicone-based polymers or forming thin film graft polymerization layers, but the characteristics of these polymers are that they are slippery, which impairs the texture. Poor adhesion with the adhesive interlining occurred, and the coloring effect was also limited, so sufficient quality could not be achieved.

In contrast to these prior art, the present inventors have achieved the present invention by further developing the surface warp by irradiation with low-temperature plasma.

When the surface of the fiber contains fine particles and is irradiated with plasma,
Part of the particles aggregate, or do they become independent particles without aggregation? J = Polymer matrix constituting the object or its decomposition (1) It has been found that bovine substances or third substances accumulate and thicken to form convex parts.

The fine particles are inert compared to the polymer matrix constituting the fiber structure in a low-temperature deodorizer, and the fine particles with an average particle size of 0.5 micrometers or less are applied to the fiber surface, to the fiber, or to the fiber structure. On the other hand, O8 old] is deposited in an amount of 1 to 10%, and then the fibers are irradiated with low-temperature plasma to form convex portions larger than the average primary particle diameter.

When the average primary particle diameter of the fine particles attached to the fiber surface is υ, the average size of the convex portions after plasma discharge treatment is 1.
1a or more, preferably 1.1a or more and 10a or less, a single or two or more granular structures are arranged in a row, forming an uneven structure in which the gaps between the convex portions become concave portions. It is something.

The principle of the present invention is not yet clear, but when inert fine particles are present on the fiber surface and irradiated with low-temperature deosma, the fine particles act as a shield for the plasma, etching progresses in the areas not covered by the fine particles, and the shape of the fine particles does not change significantly. However, depending on the electrode, its power, degree of vacuum, gas, and other plasma conditions, whether the once vaporized component or the fifth component polymerized in the plasma will recombine around the particles, or whether the particles will become nucleated. It is thought that the particles re-agglomerate to form convex portions on the surface that are thicker than the fine particles and develop a granular structure.

It was thought that the protrusions obtained in this way would have an immediate effect on the color development of the dyed product, but it was discovered that the shape of the four parts and their areas were more effective than the shape of the protrusions on the color development. Ta.

A scanning electron microscope was used to observe the uneven shape, and 600
The shape can be accurately grasped by electron micrographs taken at a magnification of 00 times (60 mm is 1 micrometer).

In an uneven structure in which the gap between adjacent convex portions exceeds 0.7 micrometers, no noticeable effect on improving color development was obtained. On the other hand, gaps of less than 0.01 micron are so large that they cannot be identified as gaps based on the resolution of the photograph.
On the contrary, products with such a densely packed surface structure had poor color development or a change in color tone, for example, making black appear to be dark blue, and were less effective. The largest area of four-part gaps is 0
．． 01-0.5 micronmeter.

In addition to the 60,000x scanning electron micrograph, 12,000.
I examined it at various magnifications such as 24,000.100,000 times,
A photograph with a magnification of 60,000 times is preferable, and the results will be explained below with reference to the needle side of the photograph.

The protrusions and depressions per 1 square micrometer (1 μm2) on the fiber surface that form the unevenness can be distinguished by the difference in shading in the photograph. When the areas of the deep parts (four parts) or the pale parts (convex parts) were measured, it was found that the color development significantly increases as the recessed part area decreases. The area of the four parts per 1 μm2 is 0.
In the region of less than 1 ltm2, the coloring property is adversely affected, and in the region of more than 0.8 pm', only the coloring was obtained to the extent that there was no difference between the unevenness containing fine particles and the unevenness not containing fine particles. According to experimental results, the preferred range is 0.
．． 15~0.76 pm2, more preferably 0.5~
It was 0.6 Bm2. The lower and upper limits of the concave area differed depending on the particle size and type.

Preferably, the convex portions forming the concave portions should have an average primary particle size of fine particles contained in the convex portions of 0.5 micrometers or less, and the height of the convex portions should be at least 0.02 micrometers. Improvement in the color development of the dyed product was not observed by naked eye observation unless it was micrometer or larger. JL in the plane direction of the fiber surface)ylT iTh and =
t×1. at n nz = h m +l J −m
-g)I 1. nff! It was similarly ineffective unless it was below the h-ron meter. The effect can be obtained whether the convex part is a single convex part, two or more convex parts connected, or a combination of the two convex parts; the smaller the particles are, the more likely they are to join together, and the larger the convex parts, the more independent the protrusions. The condition changed depending on the amount of growth, but in all cases, the four parts were connected to each other (the effect was recognized in the 71st model).
.

The present invention has, first of all, excellent glossy color depth and color clarity, and the dark color effect is far superior to that of the prior art. Furthermore, surprisingly, it has become possible to not only control the change in texture but also to provide anti-static, combustion, and other functions based on the structure of the convex portions and the differences in the substrate.

The objects of the present invention are not limited to synthetic fibers as mentioned above, but include natural fibers such as wool, cotton, linen, and silk, semi-synthetic fibers such as acetate, and rayon fibers. , q is also included. Synthetic fibers include Borienute/I/ type, polyamide type, acrylic type, polyurethane type, and other synthetic fibers, but synthetic fibers include those whose parts are copolymerized, two-component blends, and adhesives. It may be a combination of 9.

Further, it may contain surfactants, antioxidants, ultraviolet absorbers, flame retardants, colorants, matting agents, plasticizers, antistatic agents, and the like.

The fiber structure of the present invention includes one composed of the above-mentioned fibers alone or a composite/mixture of two or more types of fibers,
It is not limited to thread products such as tow, filament, yarn, etc., but may also be knitted or woven fabrics made by knitting or weaving such thread products, or non-woven fabrics, and any form of cloth-like two-dimensional material can be used. It is meant to include.

A similar effect can be obtained with a film-like product and a coated product as a conformal shape of a two-dimensional sheet-like product.

As for the manufacturing method, the present invention is obtained by first attaching fine particles onto the fiber surface of a fibrous structure, and then subjecting the fibers and structure to which the fine particles are attached to low-temperature plasma treatment. The fiber structure may be either before or after dyeing.

It is important that the fine particles used in the present invention have high synergistic activity in low-temperature plasma compared to the polymer matrix, and are made of silicon-containing inorganic particles, oxides of Group I metals of the periodic table, and/or salts thereof. Fine particles, aluminum oxide, thorium oxide, zirconium oxide, etc. are used, but when it is desired to add functionality, for example, to impart flame retardancy, tin oxide, aretimon oxide, aluminum phosphate, thorium phosphate, etc. are used. For imparting electromagnetic properties, use ferrite, for imparting dielectric properties, use barium titanate, etc., for imparting ultraviolet ray shielding and surface abrasion resistance, use titanium oxide, etc., but these may be used alone or in combination. Appropriately selected by mixing more than one species.

The fine particles used are those having an average primary particle size of less than 0.5 micron, more preferably 0.2 micron or less, and still more preferably 0.07 micron or less. For those that mainly produce a color deepening effect, it is preferable to use fine particles with a low refractive index, and from this point of view, silica is preferable.6 As for the fine particles, it is easy to use particles dispersed in a colloidal form due to their dispersibility. However, it is not limited to this.

A commonly used resin processing method can be used to apply the fine particles to the fiber surface.

For example, a resin liquid is applied to a fiber structure by a method such as padding, nupure, printing, etc., and after adjusting the adhesion amount to an appropriate amount using a mangle, etc., the fiber surface K (= J) is applied by dry heat or wet heat treatment. Ru.

If it is desired to strengthen the adhesion between the fine particles and the fibers, the adhesive resin can be applied at the same time as the fine particles are attached, or after the fine particles are attached. As this adhesive resin, a water-dispersed emulsion is easily used, and if the adhesive resin is to be attached at the same time as the fine particles, it may be of a combination that does not agglomerate with the colloidal material of the fine particles when mixed. For example, when colloidal silica is used as the fine particles, anionic or nonionic resin emulsions are preferred since cationic resin emulsions tend to aggregate with colloidal silica. Of course, Choginshiki r+
し @ t# Jlm l し σ) Flood sheet Wide 'R' Wr (one c ト 橢L) Resin processing agents such as precipitants, melt-proofing agents, water repellents, antifouling agents, water-absorbing agents, etc. In addition, in the case where an adhesive resin is applied after adhesion of the fine particles, these finishing agents may be contained in either.

Some of these processing agents are scattered by low-temperature plasma irradiation, but it is unclear whether they are polymerized in the plasma or recombined around the fine particles, but it is clear that the resin processing agents are not simply attached to the particles. It has been found that the durability during use such as washing is improved, and a coloring effect and new functional durability are also imparted.

In addition, in terms of texture, the fine irregularities obtained with low-temperature plasma containing fine particles are effective in creating a dry texture with a squeaky feel that is better than that of a mat. If preferred, it may have the opposite effect. This case can be solved by using a low-friction resin finishing agent, such as a fluorine-based polymer or a silicone-based polymer, and more preferably by adding a radically polymerizable fluorine-containing compound or silane compound to the plasma, or after plasma irradiation. By applying it, it is possible to create a wool-like texture that is smooth and has a moderately slimy feel.

Furthermore, as a method for imparting adhesion to the fibers of fine particles, it is also effective to irradiate plasma after the fine particles have arrived on the fibers, and then apply an adhesive resin. One of these methods is to attach an adhesive resin by plasma polymerization. This method has the advantage that it is possible to significantly improve durability, and at the same time, the process can be a dry process of low-temperature plasma irradiation and plasma polymerization. There are two methods for forming a resin by plasma polymerization: a method in which monomers are introduced with radicals remaining after plasma etching, and a method in which monomers are further introduced under discharge conditions after plasma etching and then plasma polymerized. be. The adhesive resin that can be plasma-polymerized is preferably one that has a relatively low boiling point and is volatile at room temperature. Examples of such substances include acrylic acid, methacrylic acid, or esters thereof, silicon compounds, and fluorine compounds.

As mentioned before, the mechanism of the formation of the uneven portion in the present invention is that the surface portion of the polymer thread or processed resin component that is not shielded by fine particles is once scattered by plasma irradiation and forms four parts. It is thought that the once vaporized component or the third component polymerized in the plasma recombines around the fine particles attached to the substrate surface, forming convex portions larger than the fine particles. Therefore, based on the above idea, in order to form many irregularities of a limited size on the fiber surface, it is extremely important to have the fine particles of i〈 exist as uniformly as possible on the fiber matrix surface. It is believed that there is. However, at the same time, if the layer of fine particles serving as a shield is thicker than necessary, etching into the interior of the substrate will be inhibited and the texture will be impaired, so it is preferable that the layer be as thin as possible.

In this respect, the amount of microparticles attached to the fiber surface is 0.001 to 10% by weight, preferably 0.005 to 10% by weight relative to the fiber.
It is best to set it at 2% of market volume. 41 If the amount is less than 0.001%, the effect of improving color development and texture will be small;
If it exceeds %, the texture will be significantly impaired. however,
Depending on the fabric weight and constituent denier of the fiber structure, it may be effective to further expand the width.

In addition, in the present invention, due to the mechanism in which a convex portion larger than the initial particle size of the adhered fine particles is formed as speculated above, the fifth substance as described above is used as a substance that covers and thickens the fine particles. Instead, we actively use materials that can be applied to C'VD and PVD, which vaporize and deposit them, such as polymers, inorganic materials, and metals that can be vacuum-deposited, sputtered, or ion-blasted. This can also be introduced into the 7° lasma region, vaporized, and deposited around fine particles to thicken them.

Plasma is a state in which high energy is given to a substance, causing its molecules or atoms to dissociate, resulting in a gas containing positive ions and an approximately equal number of anions or electrons in addition to neutral atoms. To tell. Normally low temperature plasma is 10'ro
Excited atoms, ions, electrons, etc. generated with A- by applying a high pressure of 1 h by low frequency, high frequency, or microwave to a gas atmosphere under reduced pressure below rr act on the surface of the polymer substrate. The surface is then etched. As the gas for generating low-temperature plasma, for example, oxygen, air, nitrogen, argon, helium, etc. are preferably used.

The conditions for low-temperature plasma treatment include the type and shape of the device, type of gas, current flow, degree of vacuum, output, and treatment time, etc., which are selected appropriately depending on the material, composition, shape, and desired degree of darkening of the target fibers. There is a need.

As mentioned above, the present invention forms convex parts by accumulating and thickening fine particles as nuclei, so the plasma treatment conditions include plasma irradiation without causing fine particles to adhere to the substrate surface to form irregularities on the substrate surface. It is not necessarily necessary to use intense irradiation conditions as in the case where the irradiation is performed. The technical feature of the present invention is that fine particles accumulate and thicken under mild irradiation conditions such that the substrate is etched by several millimeters, resulting in the formation of irregularities as described in the claims. .

In the article obtained by the present invention, it is not necessarily necessary that the entire front and back surfaces of the fiber structure are textured, but it is sufficient that at least one side is textured.

Therefore, in that case, it is sufficient that the fibers in the surface portion exposed on one side, and at least the surface layer thereof, are made uneven, and this is carried out by appropriately selecting plasma treatment conditions. Regarding air, oxygen, and argon as gases used to generate low-temperature plasma, in terms of color deepening effect, the order is oxygen, air, and argon.
It was found that the type of gas used also affected the effectiveness.

Furthermore, when we varied the gas flow rate while keeping the degree of vacuum constant, we found that the gas flow rate had a large effect on the unevenness formation speed.

In addition, the plasma treatment itself may be performed either before or after dyeing the fibers as described above, but if the method is performed before dyeing, the unevenness formed on the fiber surface may be deformed during the subsequent dyeing process. It is preferable to carry out the process after dyeing, as there is no risk of such problems.

Furthermore, the present invention provides a system in which low-temperature plasma irradiation is performed by coating a part of the irradiation surface of the fiber structure with a coating material different from the above-mentioned adhered fine particles to create a part to be irradiated with plasma and a part not to be irradiated with plasma. , the pattern and color of the covered part can be changed to the pattern and color of the uncovered part. In this method, the boundary between the coated area and the non-coated area is very clear, and a rare effect can be imparted to the dyed product.

Further, in the present invention, as the fibrous structure to which the fine particles are attached, a structure made of fibers whose fibers have been roughened in advance can also be used. As the fiber structure made of the fibers whose surface has been roughened in advance, for example, the polyester V
A structure made of polyester fibers that has been etched with an alkaline solution to form specific irregularities on the fiber surface.
etc. are mentioned as typical examples, but the structure is not limited to these roughened fiber structures.

Among synthetic fibers, polyester fibers are the worst in the depth and clarity of dyed colors, but the technology of the present invention has a remarkable effect of improving the degree of color deepening, comparable to polyester fibers, as described above. This technology is considered to be particularly effective for fibers. In this case, the Borienether polymer is a divalent polymer in which at least about 75% of the repeating structural units are o-o-oocQco (where 10- is a divalent polymer containing 2 to 18 carbon atoms and bonded to the adjacent oxygen atom by a saturated carbon atom). refers to a glycol dicarboxylate repeating structural unit such as a unit of an organic group (organic group). The terephthalate group may be the only dicarboxylate component of the repeating structural unit, or up to about 25% of the repeating structural unit may be adipale, sepacate, isophthalate, bibenzoate, hexahydroterephthalate, diphenoxyethane. -4,41-dicarboxylate, 5-
Other cica poxylates such as sulfoisophthalate groups 1
- may be included. As the glycols, branched chain glycols such as polymethylene boule such as ethylene glycol, tetramethylene glycol, hexamethylene glycol, etc., diethylene glycol, triethylene glycol, tetramethylene glycol, or mixtures thereof can also be used.

If desired, up to about 15% by weight of higher glycols such as high molecular weight polyethylene glycols can also be added to the stone.

Various other substances such as matting agents, gloss improvers, anti-tarnish agents, etc. may also be added to the polymerization mixture if desired.

As understood from the above explanation, the present invention aims to achieve the intended purpose by giving the fiber surface a unique structure. Not only can it be applied to fiber structures made by mixing one or more types of synthetic fibers, but it can also be applied to fiber structures made of composite fibers in which the fiber itself has a core-sheath structure or a dorsal-ventral structure. Of course.

Furthermore, the present invention can be applied to high-order processing such as false twisting and crimp processing.
Shapes similar to triangles and hexagons can be formed, and shapes such as trefoil, T-shape, 4syw, and cxmtmy can be formed due to the irregular cross-section nozzle during spinning.
It goes without saying that it may be used as a shape or a cross-sectional shape of various shapes.

The false twisted yarn according to the present invention exhibits the effect of reducing glitter. Therefore, it is advantageous in the sense that it also exhibits an anti-glitter effect on the POY D'I'Y false twisted yarn obtained by high-speed spinning.

Next, the present invention will be explained with reference to examples, but the present invention is not limited to the following examples.

As is common knowledge to those skilled in the art, structures made of polyester fibers are impregnated with titanium dioxide in the fibers to make the structure matte and to improve the texture of the structure. Therefore, the usual method is to perform a weight reduction treatment using an alkaline solution. In the following Examples and Comparative Examples of the present invention, when the target fiber material is polyester fiber, the present invention is applied to a structure using normally used semidal fibers and subjected to weight reduction treatment as described above. Although the present invention mainly discloses examples in which the present invention is applied, it is obvious that the present invention does not necessarily have to be applied to such a fiber structure.

Example 1 A polyethylene terephthalate polymer with an intrinsic viscosity of 10.69 was produced by a conventional manufacturing method, and each polymer was spun and drawn in a conventional manner to obtain a cross section of a 75 denier)v/36 filament. Each circular fiber was obtained. Next, combine each of these filaments for 15
The S-twist and 2-twist actual twist were carried out at 0 denier and 2100 times/US, and after heat setting, a chilimen georgette fabric was made using the warp and weft yarns. This fabric was embossed and heat set, and a sodium peroxide aqueous solution of 40 (1/e, 98
The weight was reduced at ℃ so that the weight loss rate was 25%.

Later, as a dye, Kayalon P from Nippon Kayakusha Tae was used.
a soil ves gloss 1゜Black G-SF 12%O,W
, f, surfactant TO manufactured by Toho Chemical Co., Ltd. was used as a dispersant.
h08alt TD O, 5f/l, pH adjuster Ultra Mt-N2 (mixture of helic acid and sodium acetate) manufactured by Daiwa Chemical Co., Ltd. 0.7 fl/l! Add 135
Stained at 8°C with hydrosulfur l-f I/l, caustic soda 1 f/l, nonionic activator 1 f/l.
Reduction and washing were performed at 0°C for 10 minutes to obtain a black dyed product.

These black-dyed fabrics have an average grain size of 15
Attach millimicron (mμ) colloidal silica,
Various silica-attached fabrics were created by varying the amount of silica attached. Colloidal silica was deposited by a bud-dry method.

The obtained various fabrics were placed in an internal electrode type plasma device, and plasma irradiation was performed for 1 to 5 minutes at a frequency of 110 KHz, using oxygen and air as introduced gases, a degree of vacuum of 0.05 to ITOrr, and an output of 50 W. . The ρ chromaticity of the obtained product was measured using a self-recording spectrophotometer manufactured by Hitachi.

The color density of the dyed product is indicated by the value shown in the display in ♂aab. As shown in the photo, measurements were taken at five locations on the surface of 1 square micrometer.The recess area referred to here refers to the area of the recess in 1 square micrometer. As can be understood from Examples 11α2 and subsequent examples, the color depth of the dyed chilimen georgette was compared to &1, which was simply irradiated with plasma.
Plasma irradiation after application significantly increases the dark color effect. Photo 1
Photo 2 is a scanning electron micrograph at a magnification of 000 times after fine particles were attached to the flat plate 6, and Photo 2 was taken after plasma irradiation. This photo 2
In the case of
-0,1/ZIF+, it can be seen that a granular structure with a major axis up to several times that length is formed. The light part of the photo shows the convex part, and the deep part shows the four parts. The area ratio of these four parts has a significant effect on color development, and the smaller the area of the concave part per 1 square/Im 2 , the more intense the color becomes. However, if it is too dense to the extent that it exceeds 0.1, the effect will be reversed.Also, if the area of the recess is too large, the color deepening effect will actually fade, and 0.8 seems to be the limit. The gap between the convex portions is in the range of 0.01 to 0.431° C.m in the range where the darkening effect is good, but in A2 it exceeds this range. Silica (: 0 in 1 coat amount)
．． It is understood that a sufficient effect is already expressed even when the concentration is 001% by weight, and 10% by weight of j610 ('j' M
Base L-h: /7-1 desired ξ catch/moh Nakata resistance 1-1 given Example 2 Vertical 50 denier/L/56 filament, horizontal 75
Silica with different average particle diameters is attached to the fabric, which is made of 72-denier filament polyethylene terephthalate filament yarn and dyed black through conventional washer, heat-setting, and alkaline weight reduction processes, and is then used as an internal electrode. Using a type continuous plasma irradiation device, the frequency was 110 KHz, the introduced gas was oxygen, and the vacuum degree was Oj 5.
Torr, irradiation residence time 50 seconds, irradiation energy i
Plasma irradiation was performed under the conditions of i (0.37 Kwh/nL (output conversion)).

The color depth of the black-dyed palace fabric of iJ due to fine particle adhesion and plasma irradiation was IA'b:=18.9. Density and scanning i after plasma irradiation! Surface mta from photomicrograph
The results were as shown in Table 2. Experiment 15.14.15
．． As is understood from 16.21.22, when the average primary particle size of the fine particles becomes large, a deep coloring effect can be obtained with a high adhesion amount, and when the particle size becomes small, even paper-backed BM is sufficiently effective. Obtained. This is understandable from the point of view of the number of microscopic particles. When the particle diameter becomes too large as shown in point 23, the deep coloring effect disappears, and rather, the phenomenon of monotony due to scattered light occurs.

As seen in J615, even with silica having a particle size of 0.045 μ771, the darkening effect was small due to the excessive area of the four parts, probably because the number of particles was too small in the amount of jtt with o, o o i in%. In terms of texture, except for A15.20.26, a squeaky feel similar to silk was obtained, giving a suitable silk-like texture.

Example 3 Commercially available wool fabrics, rayon/polyester/I/mixed yarn fabrics, and triacetate/polyester blended yarn fabrics were black-dyed by applying 0.1 weight and 11% silica using a pad-dry method, respectively. Plasma irradiation was carried out under the same conditions as in Example 1.As shown in Table 3, each fabric had an even deeper color effect.The surface of each fiber in this case was observed using a scanning electron microscope. The area of the concave portion in μnL was a concave structure of 0.5 to 0.5 μ, and the height of the concavities and convexities was in the range of 0.04 to 0.16 μ in cross-sectional observation using an ultrathin section.

In the case of wool, the lustrous taste was too emphasized, so following plasma irradiation, the temperature was changed to CHZ =CHC00C
When HzCF2CF2H vapor was introduced into the apparatus and reacted, the dull taste was reduced and it was possible to obtain a soft and extremely dark black dyed cloth. Furthermore, the surface is fluorinated, which gives it an anti-dyeing effect, and it has also been able to achieve outstanding dry cleaning durability using a series of dry systems.

Table 3 Example 4 A dark blue dyed product of 2/2 twill yarn fabric using polyethylene terephthalate 150 denier 48 filament false twisted yarn was coated with 2.0 ml of aluminum hydroxide having an average particle size of 0.1 micron. % by weight and placed in an internal electrode type plasma device at a frequency of 13.56 MHz and a vacuum of 0.05 TQtT using argon as the introduced gas.
Plasma irradiation was performed for minutes. Then, chloromethyμ dimethylchlorosilane gas was introduced and plasma irradiation was performed for 50 seconds. The initial value of the dark blue dyed product was 27, whereas the Iab value of the product that was irradiated with the plug after microparticle adhesion was 22, giving it a dark blue color with a certain bacterial strain. -The LO value, which is an indicator of flame retardancy, is 24 for the untreated product, compared to 21 for the untreated product.
was obtained, the flame retardant effect was expressed, and the frictional charging voltage test with a rotary static tester after washing 50 times was also 5.
A fabric with a lower width of 60 cm, which was larger than the untreated V, was obtained, and was rich in flame retardant and antistatic properties, as well as excellent color development.

[Brief explanation of drawings]

Photo 1 is an example of a state in which fine particles are attached to the fiber surface, and Photo 2 is an example of an uneven shape formed by plasma irradiation, and is a scanning electron micrograph taken at 60,000 times magnification. Patent Applicant: Rira Shi Co., Ltd., Patent Attorney: Suen Ken, Drawing No. 1) (No change in content) Procedural Amendment (formality) October 11, 1980 Patent Application No. 86250 2 , Title of the invention: Roughened semi-blended true fiber structure and its manufacturing method 3, Relationship with the case of the person making the amendment Patent applicant: 1621 Sakazu, Kurashiki City (108) Rira Shi Co., Ltd. Representative Director Ueno et al. - 4 Agent: 2045-1, Aoeyama, Sakazu, Kurashiki City, Rira Shi Co., Ltd. Phone: Tokyo O3 (27713182) 5.Date of amendment order (shipment date: September 25, 1980) 7, Contents of amendment (1) Specification No. 66 The description in the column "4. Brief explanation of the drawings" on page 4 is corrected as shown in Attachment 1. (2) The drawings are amended as shown in Attachment 2. Attachment 7 14. Brief explanation of the drawings Figure 1 shows the fiber surface This is a scanning electron micrograph (magnification: 600x) showing an example of a state in which fine particles are attached. Figure 2 also shows the present invention, which was produced by plasma irradiation on the surface of the fine particle-attached fiber shown in Figure 1. This is a scanning electron micrograph (magnification: 60,000 times) of the uneven shape of the surface of the fiber structure of the invention.

Claims (1)

[Scope of Claims] 1. A fiber structure made of roughened fibers in which the fiber surface is formed of convex portions containing fine particles, and the convex portions aggregate to form unevenness on the fiber surface. , in at least the surface layer portion of the fibers located at least in the surface portion of the fiber structure,
The gap between adjacent protrusions is 0.01 to 0.7 micrometers, and the area of the four parts is 1 square micrometer (l
Roughened fiber structure 2 characterized by the formation of irregularities of 0.1 to 0.8 square micrometers (Ittn2) per tm2), the average order of fine particles contained in the convex portions of the fiber surface. The particle size is 0.5 micrometers or less, the height or depth is at least 0.02 micrometers or more, and the short axis of the protrusion in the plane direction of the fiber surface is 0.05 micrometers or more, singly or separately. A roughened fiber structure 3 according to claim 1, characterized in that the fiber structure 3 is continuous with each other, and has an average primary particle size that is inert compared to the polymer matrix constituting the fiber in low-temperature plasma. fine particles of 0.5 micrometer or less on the fiber surface, 0.001 to the fiber
A method 4 for producing a roughened fiber structure, comprising a step of adhering the fine particles by 10 to 10 ii%, and a step of irradiating the fiber structure to which the fine particles are attached with low-temperature plasma to form convex portions larger than the average particle diameter. The average particle size of the fine particles attached to the fiber surface is a
The method for producing a roughened fiber T14 structure according to claim 5, wherein the average size of the convex portions after plasma discharge treatment is 1.1a or more.