JPH06102871B2 - 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 are now unsatisfactory. . 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-58-14418 are known.
There are No. 9 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 to 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 dye bleed-out, color change, etc., and improvement in darkness is limited.

Further, there is JP-B-61-35309 as a method for uniformly adhering a polymer having a low refractive index to the surface of a single fiber, not to the voids between fibers, to increase the darkness. This method 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 with this method, if the darkness degree of L ^* is 13.5 to 14.0 or less, the discoloration (frosting) due to Kosre is remarkably large, and the feeling change is also large, and the range for practical use is L ^*
= 13.5 to 14.0.

(Problems to be Solved by the Invention) The present invention provides a darkening technique capable of attaining an L ^* value of 11 to 13 without any problem in terms of various consumption performance in the above-mentioned conventional techniques. It is something to do. If the ΔL ^* value also has a difference of 0.3, it can be judged visually that it is dark and thin. Therefore, the present invention, in which the ΔL ^* value is 0.5 to 2.5 lower than that obtained by the conventional technology for practical use, can be said to be the ultimate darkening technology.

(Means for Solving Problems) In the present invention, the dyed fiber structure is coated with a resin, and the resin is a film-forming resin (A) and / or inorganic fine particles (B), and a refractive index of 1.55 or less. Of the low refractive index polymer (C), further comprising a thin film (D) containing at least a silicon-based compound on at least one surface of the resin layer, and the thin film has a thickness of 300 to 2000Å and a fiber structure thereof. It relates to a manufacturing method.

Hereinafter, the present invention will be described in detail.

The fiber structure in the present invention refers to a knitted fabric, a woven fabric, a non-woven fabric and the like made of natural fibers, synthetic fibers, 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 fiber structure is coated is composed of a film-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. That is, (A) and (B)
And (C), or (B) and (C), or (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 unevenness of the fine particles, and
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, if 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 dry cleaning resistance. .

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 dark color effect after resin processing is small, and the time required for forming a thin film is too long to provide sufficient 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 component (C) is mixed and adhered in one bath, it is necessary to combine the components so that the dispersed state of the mixed system is not impaired, and the components usable 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 tank containing a silicon compound is formed on both surfaces or one surface of the resin-processed fiber structure. A thin film tank containing a silicon compound is a thin film tank consisting of a silicon compound alone,
Alternatively, a thin film layer made of a mixture of another thin film-forming compound such as a fluorine compound and a silicon compound is shown. It should be selected depending on the product whether to attach a thin film on one side or on both sides. Even if a thin film is attached on only one side, it is possible to sufficiently darken the color and there is no practical problem.

The 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 graft method is effective from the viewpoint of effectively forming a thin film on the fiber surface. .

The silicon compound monomer of the present invention, (However, R _{1 to} R ₄ are -OCH ₃ , -OC ₂ H ₅ , CH ₃ , C ₂ H ₃ , CH ₂ = C
H, H, Or an alkoxysilane silicon compound represented by (However, R _{1 to} R ₃ are H, CH ₃ , CH ₂ = CH, Chlorosilane-based silicon compound represented by either Cl or ClCH ₂ ), or (However, Y is CH ₂ = CH, CH ₂ -CHCH ₂ O, NH ₂ , SH, Cl, Any of NHR'NH ₂ (R: alkyl group), R is an alkyl group, and X is-
OCH _3, one) silane cutlet pulling silicon compound represented by the -OC ₂ H _5, or (However, R _{1 to} R ₂ are H, CH ₃ , C ₂ H ₅ , Si (CH ₃ ) ₃ , A silazane-based silicon compound in which R is CH ₃ COSi (CH ₃ ) ₃ or CF ₃ COSi (CH ₃ ) ₃ ), or (However, R is an alkyl group, X is Cl, NH ₂ , Of any of the above), a reactive siloxane oligomer-based silicon compound. Typical examples include trimethoxysilane, trimethoxyvinylsilane, triethoxysilane, triethoxyvinylsilane, trimethoxychlorosilane, trimethylmethoxysilane, dimethoxyvinylsilane, dimethylmethoxyvinylsilane, trimethylvinylsilane, triethylvinylsilane, vinyltrichlorosilane, hexamethyldisilane. Silazane, dimethyltrimethylsilylamine,
Examples include amino siloxane and chloro siloxane.

Some of these silicon-based monomers, which have a low film-forming ability by themselves, may be used in a mixture with a small amount of hydrogen gas or non-polymerizable gas to significantly improve the film-forming rate. Therefore, the silicon compound used in the plasma polymerization method is not particularly limited. The silicon-based compound used in the discharge graft method is preferably a vinyl-based silicon compound having a C = C double bond.

The fluorine-based compound monomer used in the plasma polymerization _{method, C n H m Cl p F} 2n-mp type (n represented by _{C 2 F 4, C 3 F} 6
≧ 2, m ≧ 0, p ≧ 0, 2n−m−p ≧ 1), C
C _n H _m Cl _p Br _q F _{2n + 2-mpq} type represented by F ₄ , C ₂ F ₆ and C ₃ F ₈ (n ≧ 1, m ≧ 0, p ≧ 0, q ≧ 0, 2n + 2- p-
q _n is an integer), C _n H _m Cl _p F _{2 n-mp} ring type represented by C ₄ F ₈ (n ≧ 3, m ≧ 0, p ≧ 0, 2n−m−p ≧ 1 integer) ), A cyclic type having a double bond of C _n H _m Cl _p F _2n-2-mp represented by C ₄ F ₆ (n ≧ 4, m ≧ 0, p ≧ 0, 2n-2
-M-p ≧ 1), a type represented by C ₃ F ₆ O, N
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.

The fluorine-based compound monomer used in the discharge graft method is preferably a compound having a carbon-carbon double bond and a fluorine atom, such as C ₂ F ₄ , C represented by C ₃ F _{6. n}
H _m Cl _p F _2n-mp type (n ≧ 2, m ≧ 0, p ≧ 0, 2n-m
-P ≧ 1 integer), Type (m = 1,2, n = 1-4 integer, R ₁ : H or CH ₃ ,
R ₂ : H or F).

The plasma polymerization referred to in the present invention refers to a polymerization method utilizing low-temperature plasma discharge, and at the time of discharge, one or more kinds of the silicon-based compound monomer or a mixed monomer of the silicon-based compound monomer and the fluorine-based compound monomer is used. It is supplied and is subjected to one-step polymerization in the presence or absence of a non-polymerizable gas.

In the discharge graft method, a resin-processed fiber structure is subjected to low-temperature plasma discharge in the presence of a non-polymerization gas to generate radicals, and is introduced into an atmosphere containing at least one of the above monomers and polymerized without being exposed to oxygen so much. Or a resin-processed fiber structure is exposed to an atmosphere containing oxygen by low-temperature plasma discharge in the presence of oxygen gas or a non-polymerizable gas to change radicals to peroxides, and an atmosphere containing one or more of the above monomers. A peroxide method or the like in the case of introducing into and polymerizing is included.

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 ¹² c.
It is characterized by m ^-3 and is also called non-equilibrium plasma because it does not establish 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
At 100 Hz or less, the edge effect of the electrode is likely to occur, and arc discharge is likely to occur at the edge portion. As the current, alternating current, direct current, biased alternating current, pulse wave or the like 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 end portions of the larger electrodes are easily disturbed by the electric field, so that treatment spots are likely to occur. Therefore, in the case of a large plasma processing apparatus, an asymmetric electrode is preferable. The object to be processed can be set and moved at any position between the electrodes, but contact with one of the electrodes may result in less wrinkling and a greater processing effect.

The shape of the electrode on the side that does not come into contact with the object to be processed can be arbitrarily set to one or more such as a columnar shape or a rod shape with a polygonal cross section having an acute angle cross section, but the processing 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. Further, as the shape of the electrode on the side with which the processed material may come into contact, a drum-shaped shape, a plate-shaped shape, or a modified shape thereof can be used. It is not limited to. 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.

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 of the 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 above-mentioned monomer that is introduced into the vacuum system may be either a monomer-only gas, a monomer gas and a non-polymerizable gas, or 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, a monomer 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 into the vacuum system, and those in which the fibrous structures are placed in the preliminary vacuum system and can be moved to the processing chamber. It refers to one 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 discharge part area, the area of the fibrous structure existing in the discharge part,
Alternatively, when the plasma discharge part output value is divided by the surface area of either of the electrodes, one of the numerical values is 0.1 to 5 watts / cm ²
It should be 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. Plasma output
If it is less than 0.1 watt / cm ^2, the treatment takes time and the thickness of the thin film is not sufficient. Plasma output is 5 Watts / cm ²
When it becomes the above, discharge becomes a little unstable and etching other than polymerization is likely to occur. Plasma polymerization in the present invention,
From the viewpoint of the long-term discharge stability of the discharge graft, 0.1 watt / cm ² or more and 2 watts / cm ² or less are most preferable.

The processing time is preferably about 5 to 600 seconds, but is not necessarily limited to this range. In less than 5 seconds,
The film thickness of the polymer film is a little thin, and if it exceeds 600 seconds, the film thickness of the polymer film is sufficient, but it may be different from the original performance of the fiber due to coloring, slightly hard surface, or brittleness. .

The film does not necessarily have to be a uniform film, and may be dot-shaped or block-shaped. Darkness increases as the film thickness increases, but the film thickness must be in the range of 300 to 2000Å to obtain the highest degree of darkening. 300Å
If it is less than 2000, the effect of improving the darkness is small, and if it exceeds 2000Å, the texture becomes slightly hard. Dye transfer Sublimation prevention, water repellency,
The thickness of the thin film is preferably in the range of 300 to 1000Å from the viewpoint of improving the fastness to friction against dry heat and wet heat. 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.

Thus, a thin film having a thickness of 100 to 2000 Å in which a silicon compound or a mixture of a silicon compound and a fluorine compound is formed is formed on at least one surface of the resin-processed fiber structure.

The thin film of the silicon compound has a characteristic that the frosting property is not deteriorated because the friction coefficient is lower than that of the thin film of the fluorine compound alone. Furthermore, a thin film formed by mixing a fluorine-based compound with a silicon-based compound becomes slightly reddish black as compared with the case where the silicon-based compound alone is used, and in the field where reddish black is desired, it is significant to mix the fluorine-based compound. Furthermore, the frosting property is improved compared to the case of a fluorine-based single thin film,
Adhesion tends to be improved as the film thickness increases, as compared with a silicon-based single thin film.

It should be freely selected whether this thin film is formed on one side or both sides of the fiber structure, and even a thin film on only one side has a sufficient dark color effect, and there is no particular problem in practical use.

The sample having a thin film formed by this polymerization method can be improved in frosting property by passing through an aqueous solution, although the reason is not clear. 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 enhance the dark color effect of directly attaching the silicon-based resin processing agent to the fiber structure. This is because the adhesion of the silicon-based darkening agent to the higher the darkness is significantly impaired, the adhesion to the interlining becomes difficult. However, in the case of the present invention,
It is already a sufficiently dark material at the stage of the resin-processed fiber structure, and a thin film of a silicon-based compound is placed on it, so that it becomes a dark material that does not reduce the adhesiveness. . Moreover, in the present invention, when the thin film is formed by the plasma polymerization method or the discharge grafting method, the adhesiveness is a more excellent darkened material.

In addition, the present invention is also called "coating offset".
A polymer film of a fluorine compound is formed on the surface of the fiber to prevent migration and sublimation of disperse dyes in the fibers constituting the coated fabric (JP-A-61-186578 and JP-A-62-186578). 45
No. 784) and 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, dipped, 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 fine porosity. 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, the same dark color effect as that obtained by the thin film polymerization described in the prior art at the beginning can be obtained.

In the present invention, as described above, L ^* is 13.5 to 14.0 at the stage of the resin-processed fiber structure, on which a polymer film of a silicon-based monomer, or a polymerization of a silicon-based monomer and a fluorine-based monomer is performed. By forming a film at L ^* 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 polyester structured processed yarn was prepared, processed by an ordinary method and dyed black. The darkness of this fabric is L ^* = 1
It was 5.0.

This 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 TR-420 (urethane acrylic (A) with silicone (C) added), Shwatt N-20 (crosslinking agent), Electrostripper TA-267 (antistatic) Agent)
Was 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 a dip / nip method, and dried by a cylinder dryer and a Ron group dryer. The darkness of this fabric was ^* = 13.8. The amount of resin deposited by the two treatments was 1.5% by weight.

This fabric can be treated with methyltrimethoxysilane monomer or
Low temperature plasma polymerization was performed using C ₃ F ₆ 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 down to 5 × 10 ^-2 Torr with a vacuum pump, and each of the above-mentioned monomer gases was caused to flow 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.

Table 1 shows the L ^* values of the fabrics treated at each treatment time.

Example 2 A polyester fiber added with 3% by weight of colloidal silica having an average particle diameter of 45 mμ was formed into a woven fabric, and then a weight loss of 23% by weight was used to prepare a roughened fiber, which is a woven fabric made of Chileenzijo oseutto and subjected to usual processing. It was dyed black.

A solution was prepared so that 0.3% by weight of colloidal silica (B) having an average particle size of 15 mμ 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 in the same manner with a mixed monomer of trimethylchlorosilane / C ₃ F ₆ = 3/1 or a single monomer of C ₃ F ₆ .

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 silicon (C) are mixed in a solid content ratio of 2/3, and a solution containing an antistatic agent is further attached and dried, and then 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, vinyltrimethoxysilane monomer was added at a rate of 10 l / hour and a vacuum degree of 0.
After adjusting to 4 Torr, plasma polymerization was performed. Further, using the plasma discharge device used in Example 2 for the black dyed resin-treated fabric, argon gas 20 l / hour, vacuum degree 0.5 Torr 60
After irradiation for 2 seconds, vinyltrimethoxysilane monomer 10
Discharge grafting was performed at a vacuum degree of 0.4 Torr for 1 / hour.

Table 3 shows the case of plasma polymerized thin film in Experiment Nos. 32 to 36,
Experiment Nos. 38 to 41 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 without resin treatment was irradiated with argon and subjected to electrical discharge graft treatment with vinyltrimethoxysilanemonmer for 240 seconds, which is shown in Experiment No. 42. However, the dark color effect L ^* = 13.5 The frosting ability was 2nd grade and it was not practical.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuki Sakamoto 1621 Sakata, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd. (56) References JP-A-58-144189 (JP, A) JP-A-57-139585 (JP) , A) JP-A-59-216978 (JP, A) JP-A-61-186578 (JP, A)

Claims (2)

[Claims] 1. A dyed fiber structure is coated with a resin,
The resin comprises a film-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, and at least one surface of the resin layer is coated with at least a silicon compound. A thin film (D) containing is formed, and the thickness of the thin film is 300 to 2000Å. 2. A dyed fiber structure, a film-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 to the fiber structure. 0.5 to 3% by weight is adhered and cured, and a thin film (D) containing at least a silicon compound is formed on at least one side of the adhered and cured product by plasma polymerization or discharge grafting.
A method for producing a fiber structure, which comprises forming the film with a film thickness of 300 to 2000Å.