JPH073032B2 - Fiber structure and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a technique for darkening a dyed fiber structure.

(Prior Art) Various techniques for darkening a dyed product of a fiber structure have been studied. In particular, various technologies have been studied in the field of polyesters, which are difficult to produce dark colors.

One technology flow is a resin processing or discharge polymerization of a polymer having a low refractive index on a dyed fiber structure, and another technology flow is an alkaline solution or plasma etching on the fiber surface of the fiber structure. Is a method of roughening the surface. Among these, some are listed as darkening fiber structures, but since the darkening level in this field is advancing day by day, those darkening levels have become unsatisfactory at present. . Now, the above conventional technique will be outlined.

As a technique for resin-dyeing a polymer having a low refractive index into a fiber structure to perform deep dyeing, JP-B-58-51557 and JP-A-58-144 are known.
There is No. 189 etc. It is a fact that these techniques have some darkening effect. For example, in the case of a black cloth, the L ^* value as an index of darkness is L ^* = 15, but it is possible to set L ^* = 14 by this method. However, even if the resin adhesion amount is increased in order to further increase the darkness, the resin does not uniformly adhere to the surface of the single fiber, the resin adheres only to the inter-fiber voids, and the darkness does not increase. There are some problems such as deterioration of adhesion to the ground, discoloration due to kosher, discoloration due to dry cleaning, change in feeling, contamination due to bleed-out of dyeing, color change, etc., and improvement in darkness is limited.

Further, there is JP-B-61-35309 as a method of uniformly adhering a polymer having a low refractive index to the surface of a single fiber instead of a void between fibers to increase the darkness. This technique is effective as a technique for uniformly adhering the resin to the surface of the single fiber present on the surface of the fiber structure by plasma polymerization or discharge graft polymerization. According to this method, setting L ^* = 15 to L ^* = 10 or less is not impossible experimentally, and is effective as a method for enhancing the dark color effect. However, even in this method, L ^* with a darkness of 13.5 to 14.0 or less has a significantly large discoloration (frosting) due to Kosure, and the change in texture is also large, and the range for practical use is still
The L ^* was in the range of 13.5 to 14.0.

(Problems to be Solved by the Invention) The present invention does not provide a darkening technique capable of reaching an L ^* value of 11 to 13 in addition to the above-mentioned problems in terms of consumption performance in the conventional technique. It is what

If there is a difference of 0.3 in the ΔL ^* value, it is dark with the naked eye, and thinness can be sufficiently judged. Therefore, it can be said that the present invention, in which ΔL ^* is 0.5 to 2.5 lower than that obtained by the conventional practical application technology, is exactly the ultimate darkening technology.

(Means for Solving Problems) In the present invention, the dyed fiber structure is coated with a resin layer, and the resin layer contains the coating-forming resin (A) and / or the inorganic fine particles (B) and a refractive index of 1.55 or less. Low refractive index polymer (C)
And a thin film (D) of a fluorine-based compound is formed on at least one surface of the resin layer, and the thickness of the thin film is
The present invention relates to a fiber structure having 100 to 2000Å and satisfying 0.2 ≦ α = F / C ≦ 1.8, and a method for producing the same.

Hereinafter, the present invention will be described in detail.

The fiber structure in the present invention means natural fiber, synthetic fiber,
It refers to a knitted fabric, a woven fabric, a non-woven fabric, etc. made of semi-synthetic fibers and recycled fibers. The present invention is particularly effective for a polyester fiber structure having poor dark color.

The resin with which the fibrous structure is coated comprises the film-forming resin (A) and / or the inorganic fine particles (B) and the low refractive index polymer (C) having a refractive index of 1.55 or less. That is, if it consists of (A), (B) and (C), or (B) and (C)
It includes a case consisting of and or a case consisting of (A) and (C).

The film-forming resin (A) plays a role of a binder that holds the inorganic fine particles and the low refractive index polymer to the fiber structure. Compared to the case without (A), the film-forming resin has discoloration due to discoloration due to washing, dry cleaning, and abrasion. It is very effective as a counter and at the same time acts as a texture adjustment. In addition, a polymer having a relatively low refractive index is also important from the viewpoint of exerting a dark color effect, and a polymer having a relatively low refractive index is desirable. For example, polyamide, polyacrylamide, polyurethane, polyurethane acrylic and the like are preferable, but other polymers can be used as long as they have a film forming property.

The inorganic fine particles (B) may be fine particles having an average particle diameter of 0.1 μ or less, and preferably have a low refractive index and an average particle diameter of 0.05 μ or less so as not to impair darkening.
Colloidal ones and sol ones are easy to use because they have good dispersibility and do not aggregate, and examples thereof include colloidal silica and alumina sol.

The inorganic fine particles (B) may be added to the fiber structure at once by adding them to the mixed system of (C) or (A) and (C), but the inorganic fine particles may be previously attached to the fiber structure. After that, it is preferable to adhere (C) or (A) and (C). In the latter case, the resin component is relatively uniformly attached to the fiber surface with the fine particles as the core, and further the resin (A) is attached along the irregularities of the fine particles to form the resin (A).
This is because the unevenness structure causes an increase in darkness.

The low refractive index polymer (C) having a refractive index of 1.55 or less is particularly effective when the dark color effect is insufficient in the resin processing of (A) or (A) and (B). Representative polymers include silicon-based or fluorine-based polymers, and dimethyl silicon and amino-modified silicon are particularly preferable. However, when the weight ratio of the polymer (C) exceeds 80% by weight of the total amount of the resin, problems occur due to a change in feeling, a decrease in adhesiveness with the interlining material, and a dry cleaning resistance. Therefore, it is preferably 80% by weight or less.

The total amount of resin is preferably 0.5 to 3% by weight based on the fiber structure. If it is less than 0.5% by weight, the darkening effect after resin processing is small, and it takes too much time to form a thin film in order to sufficiently impart the darkness of the final product, which is not economical. On the contrary, if it exceeds 3% by weight, it is not preferable in terms of feeling. As this resin processing method, an ordinary resin processing method can be applied, but a dip or nip method is simple and desirable.

Furthermore, with the above-mentioned component (A) and / or component (B),
When the (C) component is mixed and adhered in a single bath, a combination that does not impair the dispersed state of the mixed system is necessary, and the components that can be used as (A), (B) and (C) May be restricted. Therefore, as described above, for example, a multi-step treatment in which (B) is first attached and then (A) and (C) are attached is desirable. This multi-step treatment is also important in the sense that the resin is uniformly attached to the fiber surface. The darkness is improved in each case when it is applied 2 to 4 times, but the effect is small even if it is applied 5 times or more.
The darkness after resin processing is L ^* value = 15.0 before resin processing.
It is desirable that the (black woven fabric) grade be processed to have an L ^* value of about 13.5 to 14.0. Needless to say, the resin may contain an antistatic agent, a penetrating agent, an antifoaming agent, a crosslinking agent, a silane coupling agent, and other commonly used agents.

A thin film layer of a fluorine compound is formed on both sides or one side of the resin-processed fiber structure. Whether the thin film is applied on one side or on both sides should be selected depending on the product. Even if the thin film is applied only on one side, a sufficiently dark color can be obtained and there is no practical problem.

When a thin film layer of a fluorine compound is formed by a low temperature plasma polymerization method, the fluorine compound monomer introduced into the system during the polymerization at the low temperature plasma is excited into various states, decomposes, and polymerizes. It causes a reaction to form a main chain, or a branched structure or a crosslinked structure. The elimination of fluorine is considered to play a very important role in these reactions.

Activated carbon obtained by desorption of fluorine reacts with oxygen by taking in residual air in the system or by contacting with air when the sample after polymerization is taken out of the system.

The present inventors have found that X-ray photoelectron spectroscopy (X-ray Photoelectron
n Spectroscopy; hereinafter abbreviated as XPS), various thin films were examined, and it was found that a fluorine-based polymer with 0.2 ≦ α ≦ 1.8 was most effective in terms of the dark color effect. Here, α is a value obtained by dividing the number of fluorine atoms calculated from the peak area of fluorine F _IS measured by XPS by the number of carbon C _IS atoms similarly measured. α <0.2
In that case, the ratio of fluorine atoms to carbon is too small and the polymer tends to have a large refractive index, and the effect of dark color is small. α> 1.
In the case of 8, it becomes a polymer that is easily charged, it is very difficult to reduce the frictional electrification voltage, and the adhesiveness with the interlining is also reduced.

Means for forming a thin film is not limited to the plasma polymerization method, and there are so-called resin processing method and discharge graft method, but the plasma polymerization method or discharge glift method is effective from the viewpoint of effectively forming a thin film on the fiber surface.

A fluorine-based compound monomer used in the plasma polymerization _{method, C 2 F 4, C 3} CnHmClpF 2 n-m-p type represented by _{F 6 (n ≧ 2, m} ≧ 0, p ≧ 0,
2n−m−p ≧ 1), CnHmClpBrqF ₂ n + 2-m−p−q type (n ≧ 1, m) represented by CF ₄ , C ₂ F ₆ , and C ₃ F _8.
≧ 0, p ≧ 0, q ≧ 0, an integer of 2n + 2-m−p−q ≧ 1, and a CnHmClpF ₂ n−m−p cyclic type represented by C ₄ F ₈ (n ≧ 3, m ≧ 0) , P ≧ 0, an integer of 2n−m−p ≧ 1, and a cyclic type having a double bond of CnHmClpF ₂ n-2-m−p represented by C ₄ F ₆ (n ≧ 4, m ≧ 0, p ≧ 0, 2n
-2-m-p ≧ 1), type N represented by C ₃ F ₆ O
There are various types such as those represented by F ₃ , SF ₆ , and WF ₆ .

Deposition rate among these large industrial preferred are _{C 2 F 4, C 3 F} 6, C 3 F 8, C 4 F 8, C 3 F 6 O, in C ₂ H ₄ F ₂ or the like However, C ₃ F ₆ , C ₄ F ₈ and C ₃ F ₆ O are more preferable from the viewpoint of transportation safety and film formation rate.

Further, among these fluorine-based compounds, there are some which have a low film-forming ability by themselves, but when the mixture is mixed with a small amount of hydrogen gas or non-polymerizable gas and plasma-polymerized, the film-forming rate is remarkably improved. As mixing remarkably improved film forming rate of the hydrogen _{gas, CF 4, C 2 F 6} , C 3 F 8, C 2 H 4 F 2 are typically formed by mixing a non-polymerizable gas C ₂ F ₄ , C ₃ F ₆ , C ₄ F ₈ , C ₃ F ₆ O, etc. are typical examples of those that improve the film speed.

Among the non-polymerizable gases, inert gases have a large effect, and argon gas is particularly effective. The fluorine-based compound may contain atoms such as hydrogen, chlorine and bromine.

Further, the fluorine-based compound monomer used in the discharge grafting method is preferably a compound having a carbon-carbon double bond and a fluorine atom, such as CnF typified by C ₂ F ₄ and C ₃ F _6.
HmClpF ₂ n-m-p type (n ≧ 2, m ≧ 0, p ≧ 0, 2n
-M-p≥1), (M = 1,2, n = 1-4 integer, R ₁ : H or CH ₃ , R ₂ : H or
There is F etc.

The plasma polymerization referred to in the present invention refers to a polymerization method utilizing low-temperature plasma discharge, and refers to a case where one or more kinds of monomers are supplied at the time of discharge to carry out one-step polymerization in the presence or absence of a non-polymerizable gas.

The discharge graft method is a resin-processed fiber structure that is plasma-discharged at low temperature in the presence of a non-polymerization gas to generate radicals, and is introduced into an atmosphere containing one or more polymerizable monomers without being exposed to oxygen so much that polymerization is performed. Or, the resin-processed fiber structure is subjected to low-temperature plasma discharge in the presence of oxygen gas or non-polymerizable gas and exposed to an atmosphere containing oxygen to change radicals to peroxides, and one or more polymerizable monomers are added. Including the peroxide method and the like in the case of introducing into an atmosphere containing and polymerizing.

The low-temperature plasma means that the plasma generated during the discharge has an average electron energy of 10 eV (10 ⁴ to 10 ⁵ K) and an electron density of 10 ^{9 to} 12
It is characterized by ¹² cm ¹³ , and is also called non-equilibrium plasma because it does not have an equilibrium between electron temperature and gas temperature. Electrons, ions, atoms, molecules, etc. are mixed in the plasma generated by the discharge.

As a power source for applying electric power, an arbitrary frequency power source can be used. From the viewpoint of discharge continuity and uniformity, 1KHz to 10GHz
Is desirable. From the viewpoint of plasma uniformity in the width direction of the electrode, 1 KHz to 1 MHz is preferable, and if it is 1 MHz or more and the length of the electrode exceeds 1 m, treatment unevenness is likely to occur in the length direction. Also
Below 100 Hz, the edge effect of the electrode is likely to occur, and arc discharge is likely to occur at the edge portion. Also, the current is alternating current,
Direct current, biased alternating current, pulse wave, etc. can be used. Electrodes are divided into an internal electrode system arranged inside the vacuum system and an external electrode system arranged outside the vacuum system. In the external electrode system, when the size of the device becomes large, plasma moves especially to the surface of the object to be processed. The treatment effect is small because the activity is lost in the meantime or the plasma is scattered and the plasma concentration is diluted.
On the other hand, in the internal electrode method, the discharge electrode can be installed near the object to be processed, and therefore the processing effect is large as compared with the external electrode method.

The electrode shape is divided into symmetrical and asymmetrical. In the case of a large-sized plasma processing apparatus, which has a large processing width of an object to be processed and thus requires a large electrode, the symmetrical electrode has more demerits. For example, it is almost impossible to evenly flow the gas between the large electrodes, and the electric field is disturbed at the ends of the larger electrodes, so that processing spots are likely to occur. Therefore, in the case of a large plasma processing apparatus, an asymmetric electrode is preferable. Although the object to be processed can be set and moved to any position between the electrodes, contact with one of the electrodes may result in less wrinkling and a greater processing effect.

The shape of the electrode on the side not in contact with the object to be processed can be arbitrarily selected such as a columnar shape or a rod-like shape having a polygonal cross-section with an acute cross section, but the treatment effect depends on the number of electrodes. In contrast, if it is too small, the treatment effect will be small. The shape is preferably cylindrical. As the shape of the electrode on the side with which the object to be processed may come into contact, a drum shape, a plate shape, or a deformed shape thereof can be used. It is not limited to these. The material of the electrode may be metal such as stainless steel, copper, iron and aluminum, and may be coated with glass, ceramics or the like, if necessary. Of course, these electrodes may be water-cooled if necessary, and the cooling temperature is appropriately selected depending on the object to be treated. The cooling water is preferably water containing as few impurities as possible, but this is not particularly the case when electric leakage due to these impurities is not a serious problem.

Next, the gas to be introduced into the vacuum system should be introduced while being distributed as needed by providing a supply port as far as possible from the exhaust port by a vacuum pump. It may also be introduced between the electrodes. This is important in the sense of avoiding the gas short bath in the vacuum system, and at the same time, it is important not to cause the processing unevenness of the object to be processed.

The gas containing the monomer introduced into the vacuum system may be any of a monomer gas, a monomer gas and a non-polymerizable gas, and a monomer gas and a polymerizable gas. The monomer gas may be a gaseous one or a liquid one at room temperature.
The mixture of the non-polymerizable gas or the polymerizable gas and the monomer gas can be arbitrarily selected depending on the reactivity of the monomer gas, the performance of the formed thin film and the like. Monomer gas and monomer gas and other gases can be introduced separately into the vacuum system and mixed in the system, or they can be mixed in advance and introduced at the same time without any problem.Discharge with non-polymerizable gas Below, monoger gas may be introduced.

The degree of vacuum that causes low-temperature plasma is usually 0.001
Although about 50 Torr is used, 0.01 to 50 Torr is preferable according to the results of the study by the present inventors. When the degree of vacuum is 0.01 Torr or less, the mean free path of ions and electrons increases and the energy of accelerated particles increases, but the total number of accelerated particles that reach the object to be processed is small, and the processing efficiency is somewhat low. Moreover, a vacuum pump with an extremely large displacement is required to keep the large processing chamber at 0.01 Torr or less while introducing gas.
It is not desirable from the viewpoint of equipment cost. Vacuum degree
Above 5 Torr, the mean free path of ions, electrons, etc. becomes small, the energy of the accelerating particles becomes small, and the processing efficiency becomes low despite the large number of accelerating particles.

Further, although the relative position of the fibrous structure arranged between the electrodes has been described above, the treatment efficiency is generally good when the fibrous structure is arranged in contact with one of the electrodes. Also, if you do not want to apply much tension to the structure or if you do not want to wrinkle the structure, place the structure and the electrode on the drum electrode, for example, place the structure in contact with the drum electrode. It is desirable to move the structure while rotating the drum. In fact, minute wrinkles often cause treatment spots. When it is not necessary to pay much attention to tension and wrinkles, the structure may be placed in contact with the plate electrode, and the structure may be slid over the electrode and moved. Of course, after the one-sided treatment, the two-sided treatment can be performed by passing the electrode in the opposite position to the structure. In the usual case, the treatment effect on only one side is often sufficient, so this type is desirable from the viewpoint of treatment efficiency. However, if it is inevitable to obtain the treatment effect on both surfaces with only one pair of electrodes, the fibrous structure may be arranged at a position between both electrodes and the structure may be moved. In this case, the treatment effect is generally small as compared with the case where the electrodes are arranged in contact with the electrodes.

Next, in terms of processing uniformity, both electrodes must be held in parallel and must be arranged at right angles to the direction of travel of the fiber structure material to be processed. If this condition is not satisfied, processing unevenness will occur in the width direction of the structure.

Furthermore, the width of both electrodes must be at least 5 cm longer than the width of the fiber structure to be treated. This is to eliminate the non-uniformity of the electric field at the ends of the electrodes. If the length is 5 cm or less, the treatment effect is different as compared with the width direction of the structure, especially on both sides near the center, which is not preferable.

The equipment is capable of continuously moving and processing fibrous structures in the atmosphere in the vacuum system, those in which fibrous structures are placed in the preliminary vacuum system and can be moved to the processing chamber, and further the fibrous structure in the processing chamber. The term refers to things in which objects are arranged by partitioning, but in short, it is sufficient if the fibrous structure can move continuously. The plasma output is preferably 0.1 to 5 watts / cm ² as the output acting on the discharge part. In this case, as the area of the discharge part, when the value of the plasma discharge part output is divided by the area of the fibrous structure existing in the discharge part or the surface area of either of the electrodes, one of the numerical values is 0.1 to 5 watts / It should be cm ² . The output of the discharge part can be easily calculated by measuring the voltage and current of the discharge part, but as one guide, it may be considered to be 30 to 70% of the output of the plasma power supply. If the plasma output is less than 0.1 watt / cm ² , it takes a long time to process and the thin film is not thick enough. When the plasma output is 5 watts / cm ² or more, the discharge becomes slightly unstable, and etching other than polymerization is likely to occur. Based on the long-term discharge stability of fluorine-based plasma polymerization and discharge graft,
Watt / cm ² or more 2 watt / cm ² or less is most preferable.

The processing time is preferably about 5 to 600 seconds, but is not necessarily limited to this range. If the treatment is performed for less than 5 seconds, the thickness of the polymer film will be slightly low, and if it exceeds 600 seconds, the thickness of the polymer film will be sufficient, but coloring, slightly hard surface, and brittleness will result in the original performance of the fiber. May be different.

The non-grounded electrode referred to in the present invention is one in which the discharge electrode and the discharge circuit are insulated from the grounded can body and are in a non-grounded state. In this case, the electrode potential in contact with the sheet-like structure is different from the potential of the can body (ground potential because it is grounded), the can body does not act as an electrode, and the discharge is mainly between both electrodes. Get off. Therefore, the plasma acts on the fiber structure without being diluted effectively, and the treatment effect is significantly improved. At the same time, the treatment effect is significantly larger than that of the conventional grounding method with a small discharge power, and the predetermined effect can be achieved in a short treatment time. Therefore, the size of the apparatus can be reduced, that is, the facility cost can be reduced, and the discharge power can be reduced, so that the running cost can be reduced to a fraction.

The thickness of the thin film is preferably 100-2000Å. The film does not necessarily have to have a uniform film shape, and may have a dot shape or a block shape. Although the darkness increases as the film thickness increases, it is more preferably 300 to 2000Å to obtain the highest degree of darkening. If it is less than 100Å, the effect of improving the darkness is small, and the texture exceeding 2000Å tends to be slightly hard, resulting in poor frosting (cosrea tarnish discoloration). From the viewpoint of processing speed, 300 to 1000Å is more preferable. Further, from the viewpoints of preventing migration and sublimation of dye, water repellency, and fastness to rubbing against dry heat and wet heat, 300 to 1000Å is most preferable. The film thickness was measured by placing a polyester film in a plasma polymerization atmosphere, placing a cover glass on the polyester film for processing, then removing the cover glass, and measuring the step difference by a multiple interference microscope or an electron microscope. Also, in the case of discharge graft polymerization, the film thickness in the case of dot-like or block-like processes performed according to this can be said to be the height of the dot-like or block-like convex portions.

As described above, when the thin film is polymerized under low temperature plasma, the fluorine compound monomer introduced into the system is excited into various states and decomposed to cause a polymerization reaction to form a main chain, or It forms a branched structure or a crosslinked structure. The elimination of fluorine is considered to play a very important role in these reactions.

Activated carbon obtained by desorption of fluorine reacts with oxygen by taking in residual air in the system or by contacting with air when the sample after polymerization is taken out of the system.

It is easily estimated that the thin film synthesized from the fluorine compound monomer always contains oxygen under the low temperature plasma.
This phenomenon is an important factor in maintaining and improving the adhesiveness.

A thin film with small α = F / C by XPS analysis, that is, a film with a large amount of fluorine desorbed, reacts with oxygen inside and outside the system because a large amount of activated carbon remains at the same time as crosslinking and branching proceed. The amount increases.

The equipment used for measuring the F / C ratio by X-ray photoelectron spectroscopy, which is abbreviated as XPS or ESCA, is Shimadzu ESCA750.
Therefore, ESPAC-100 was used for the analysis.

A thin film formed on a polyester film was punched out to a diameter of 6 mm together with the film, attached to a sample stand with a double-sided tape, and used for analysis. The source is MgKa line (1253.6eV),
The degree of vacuum in the device was 10 ⁻⁷ Torr.

Measurement is performed for C _IS and F _IS peaks and each peak is ESPA
Using C100 (based on the correction method by JHScofield), perform correction analysis and obtain each peak area. The area obtained is C _IS
Is multiplied by the relative intensity of 1.00, and F _IS is multiplied by 4.26, and the surface area (fluorine / carbon,
The oxygen / carbon) atomic number ratio is calculated.

The charge correction was performed based on the Au4f7 / 2 spectrum (83.8 eV) of the gold vapor deposition film on the sample.

By passing the sample with the degree of thin film polymerization in an aqueous solution,
Although the reason is not clear, the frosting property can be greatly improved. It is also possible to further improve the frosting property by adding a softening agent, an antistatic agent, a penetrating agent, etc. for adjusting the feeling to the aqueous solution.

Conventionally, no attempt has been generally made to directly attach a fluorine-based resin processing agent to a fiber structure to enhance the dark color effect. This is because if a fluorine-based darkening agent is attached to improve the degree of darkness, the antistatic performance is significantly impaired, and the adhesion of dust increases significantly, making it unusable.
However, in the case of a thin film as in the present invention, sufficient antistatic properties can be obtained by slightly increasing the amount of antistatic agent during resin processing.

In addition, the present invention is also called "coating offset".
A polymer film of a fluorine compound is formed on the surface of the composition to prevent migration and sublimation of disperse dyes in the fibers constituting the coated fabric (JP-A-61-186578 and JP-A-62-186578).
45784) different technology.

The coating resin layer in the coated fabric is a relatively thick resin layer of acrylic, polyurethane, rubber, vinyl chloride or the like having waterproofness, breathability and moisture permeability, and is 3% by weight or more based on the fiber structure. It is applied by laminating method, coating method, dipping method, and nip method so as to cover or fill the voids of the fabric with the resin layer.In order to further increase the water pressure resistance and maintain the moisture permeability, the resin layer has microporosity. Although there are many cases that have, in any case, the resin layer is thickly placed on the fiber structure, and there is almost no darkening effect of the fabric at this stage, and the fabric is made of a fluorine-based compound. Even if a thin film is formed, only the same darkening effect as in the case of the dark color effect only by thin film polymerization described in the prior art at the beginning can be obtained.

In the present invention, as described above, the L ^* value is 13.5 to 14.0 at the stage of the resin-processed fiber structure, and the polymer film of the fluorine resin is formed on the L ^* value so that the L ^* value is 11%. The resin to be placed on the fiber structure for that purpose is as small as 3% by weight or less, and thus the resin covers the voids of the fiber structure, It is intended to be evenly placed on the surface of the monofilament without being filled up, and for that reason and also for that purpose, a specific combination component is required. It is different from Teddoff Abrik.

As described above, according to the present invention, the resin processing is performed twice or more so as to uniformly apply the resin processing to the surface of the fiber, and a thin film having a specific structure is formed on the surface of the fiber structure. The present invention makes it possible to realize a fiber structure having good dye transfer sublimation prevention properties, water repellency, and adhesive properties without any problem in terms of consumption performance.

(Example) An example will be described below.

The darkness was evaluated by L ^* a ^* b ^* with a Hitachi spectrophotometer 303.

Dye transfer preventive property is that the plasma-polymerized surface of the sample and the same type of white background resin-processed cloth are in close contact and immersed in water, taken out and the excess water is removed with a paper filter, then scissors on a stainless steel plate, 100 g / cm 80 in the atmosphere of 120 ℃ under the load of ²
Every minute, the degree of contamination on a white background was judged on a gray scale.

Water repellency was evaluated according to JIS L-1092 (spray method). Frosting was graded based on the change in concentration of the sample after the fastness to dry friction (JIS L-0849).

Adhesiveness was measured by adhesion to the interlining and peel strength. As for the bonding method, the sample and interlining are layered, and the load is 170g / 150 ° C (30 seconds).
It was heat-treated at cm ² . The peeling method is JIS L-1086
It was done according to.

Example 1 A back satin amundsen fabric for a formal black made of a polyester structure processing system was prepared, processed by an ordinary method and dyed black. The darkness of this fabric is L ^* = 1
It was 5.0.

This woven fabric was treated with Kao Corporation resin twice. The first treatment was to dip and nip the woven fabric in an aqueous solution prepared by adjusting Shwatt A-10 and Shwatt N-20 (crosslinking agent) to a solution concentration of 10% and 0.01%, respectively, and using a cylinder dryer and a pin tenter. And dried. In the second treatment, the fabric was treated with Shwatt TB-420 (urethane acrylic (A) with silicone (C) added), Shwatt N-20
(Crosslinking agent) and Electrostripper TA-267 (antistatic agent) were adjusted to a solution concentration of 4%, 0.2% and 1.0%, respectively, and treated with acetic acid to adjust the pH to 5 by the dip and nip method. Then, it was dried by a cylinder dryer and a Ron Group dryer. The darkness of this fabric was L ^* = 13.8. The amount of resin deposited by the two treatments was 1.5% by weight.

This fabric was low temperature plasma polymerized with a C ₃ F ₆ O monomer. The plasma polymerization apparatus has a power supply frequency of 200 KHz, electrodes composed of rod-shaped electrodes and drum-shaped electrodes, both electrodes being non-grounded electrodes insulated from the can body (ground). The inside of the can was pulled to 5 × 10 ^-2 Torr with a vacuum pump, and a gas of C ₃ F ₆ O was flown to 0.2 Torr. In this state, the output of the high frequency power source was increased to start plasma polymerization, and the drum was brought to a predetermined speed.

The L ^* of the fabric treated at each treatment time is shown in Table 1. As the film thickness increases, the dark color effect increases and the water repellency also improves. It can also be seen that the adhesiveness is improved after the resin processing. These darkened structures had no change in color after dry cleaning, had sufficient chargeability, and had good frosting.

In Experiment No. 3, the film thickness was 100 μm or less and the dark color effect was small, and in No. 10, the dark color effect was sufficient, but the texture was slightly hard. As a comparative example, the black dyed product subjected to the plasma polymerization treatment for 120 seconds had L ^* = 13.8, which was about the same as the color obtained only by resin processing. Also
The product treated for 180 seconds had L ^* = 13.5, but the discoloration due to Kosre was remarkable and it was not usable as clothes.

Example 2 A polyester fiber added with 3% by weight of colloidal silica having an average particle diameter of 45 mu was used as a woven fabric, and then a weight reduction of 23% by weight was performed to prepare a Kreponge yoozette woven fabric made of roughened fibers and subjected to usual processing. Dyed in black.

A solution was prepared so that 0.3% by weight of colloidal silica (B) having an average particle size of 15 mu and a penetrating agent were adhered to this woven fabric, dipped, dipped and dried. Furthermore, 1.5% by weight of a mixture of polyurethane acrylic (A), dimethyl silicone (C), silane coupling agent, antistatic agent, cross-linking agent, and defoaming agent was squeezed onto the woven fabric and squeezed. I set it up.

Then, in the same apparatus as in Example 1, plasma polymerization was carried out by changing the treatment time with a C ₃ F ₆ monomer. The fabric of Experiment No. 18 was further dipped in water containing 0.1% of silicone softener and dried. This is No. 21 and the results are summarized in Table 2. No. 22 is the one in which the drum electrode of the plasma polymerization apparatus was treated with a ground electrode having the same potential as the can body. As the processing time increases, the film thickness increases and the darkness improves. When the film thickness of Experiment No. 13 is 100 Å or less, improvement in darkness and water repellency is small. Experiment No. 20 with a film thickness of 2200Å showed little change in texture, but discoloration due to frosting was grade 2 to 3 and was somewhat poor. No.18 wet treated product N
Other performance of o.21 was the same as No.18, and the frosting was improved. The plasma polymerized film also improved the adhesiveness, which was significantly reduced by the resin processing. No. 22 is plasma-polymerized with a grounded electrode, but it can be seen that the film forming ability is significantly worse than No. 17.

Example 3 A Kasidos woven fabric for student clothes made of a 50/50 blended product of polyester and wool was prepared and black-dyed by a usual process.

To this fabric, silica (B) having an average particle size of 0.1μ
And amino-modified silicone (C) are mixed in a solid content ratio of 2/3, and a solution added with an antistatic agent is attached to the mixture, dried, and dried at 120 ° C and heat cured at 160 ° C to obtain a solid content.
1.2 wt% was adhered. Then, in the same manner as in Example 2, C ₃ F
The monomer of ₆ was adjusted to a vacuum degree of 0.4 Torr at 10 l / hour, and plasma polymerization was performed. Further, using the plasma discharge device used in Example 2, the black dyed resin processed fabric was irradiated with argon gas at 20 l / hour and a vacuum degree of 0.5 Torr for 60 seconds, and then C ₃ F ₆
The discharge grafting was carried out at 10 l / hour of the above monomer and a vacuum degree of 0.4 Torr.

Table 3 shows the case of plasma polymerized thin film in Experiment Nos. 25 to 29,
Experiment Nos. 31 to 34 show the case of the discharge graft thin film.

These products according to the present invention were excellent in the effect of dark color, were of practical quality in other consumption performances, and had sufficient dry cleaning resistance. For comparison, the sample after black dyeing was irradiated with argon and subjected to a discharge graft treatment with a C ₃ F ₆ monomer for 240 seconds, which is shown in Experiment No. 35. The dark color effect L ^* = 13.5 indicates that the frosting property is no longer 2 It did not endure class and practical use.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Keiji Fukuda 1621 Sakata, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd. (56) References JP-A-58-144189 (JP, A) JP-A-60-17190 (JP) , A) JP-A-62-45784 (JP, A) JP-A-59-216978 (JP, A)

Claims (5)

[Claims] 1. A dyed fiber structure is coated with a resin layer, and the resin layer comprises a coating forming resin (A) and / or inorganic fine particles (B), and a low refractive index polymer (C) having a refractive index of 1.55 or less. Further, a thin film (D) of a fluorine-based compound is formed on at least one surface of the resin layer, the thickness of the thin film is 100 to 2000Å, and 0.2 ≦ α = F / C ≦ 1.8 is satisfied. A fiber structure characterized by the above. Where α is X-ray photoelectron spectroscopy
The number of fluorine atoms calculated from the peak area of fluorine F _IS measured by ectroscopy)
It is the value divided by the number of carbon atoms calculated from the peak area of _IS . 2. The coating forming resin (A) is one kind selected from polyamide, polyacrylamide, polyurethane and polyurethane acryl, and the inorganic fine particles (B) are 0.1 μm.
Silica or alumina having the following average particle diameter, the low refractive index polymer (C) having a refractive index of 1.55 or less is a silicon-based or fluorine-based polymer, and the total resin amount is 0.5% by weight based on the fiber structure. The fiber structure according to claim 1, which is ˜3% by weight. 3. A dyed fiber structure, a coating forming resin (A) and / or inorganic fine particles (B), and a refractive index of 1.55.
The following low-refractive-index polymer (C) is adhered and cured to the fiber structure in an amount of 0.5% to 3% by weight, and a thin film of a fluorine compound is formed on at least one surface of the adhered cured product by a plasma polymerization method or a discharge graft method. The method for producing a fiber structure is characterized in that the film is formed with a film thickness of 100 to 2000Å. 4. The coating forming resin (A) is one kind selected from polyamide, polyacrylamide, polyurethane and polyurethane acryl, and the inorganic fine particles (B) are 0.1 μm.
The colloidal silica or alumina sol having the following average particle diameter, and the low refractive index polymer (C) having a refractive index of 1.55 or less is a silicon-based or fluorine-based polymer. Of manufacturing the fiber structure of. 5. The resin for forming the coating (A) and / or the inorganic fine particles (B) and the low refractive index polymer (C) having a refractive index of 1.55 or less are processed separately in 2 to 4 times. The method for producing a fiber structure according to claim 3 or 4.