JPH0192478A - Fiber structure and its production - Google Patents

Abstract

PURPOSE: To produce a fiber structure excellent in hyperchromic effects and durability by forming a specific film comprising a film-forming resin and/or inorganic fiber particles, a specific polymer and further a fluorine-based compound on a dyed fiber fabric. CONSTITUTION: This fiber fabric expressing excellent hyperchromic effects is produced by adhering a film-forming resin (e.g. a polyamide, a polyacrylamide, etc.), and/or inorganic fine particles, e.g. silica or alumina having <=0.1 μ average particle size and a polymer having a low refractive index (e.g. a silicone or a fluorine-based polymer). In this case, it is preferable to carry out a multistage treatment by adhering at first the inorganic fine particles and successively adhering the film forming resin and the low refractive index-having polymer, then, forming a thin film comprising a fluorine-based polymer and having 100-2000 Å, especially satisfying 0.2<=α=F/C<=1.8 (α is a number of fluorine atoms/a number of carbon atoms) by a plasma polymerization method, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Minute Hand) The present invention relates to a technique for deepening the color of dyed fiber structures.

(Prior Art) Various techniques for darkening dyed fiber structures have been extensively studied.Particularly in the field of polyester, which is difficult to produce deep colors, all kinds of techniques have been studied.

One method of technology is to resin-process or discharge polymerize a polymer with a low refractive index to a dyed fiber structure, and another method is to apply an alkaline solution or plasma to the fiber surface of the fiber structure. This is a method of roughening the surface by etching. Among these, there are some that are being listed on the market as darkened fiber structures, but because the level of darkening in this field is progressing rapidly, the level of darkening of these products is currently considered unsatisfactory. It has become.

The above-mentioned prior art will now be summarized.

Japanese Patent Publication No. 58-51557 and Japanese Unexamined Patent Application Publication No. 58-144189 are known as techniques for dyeing fiber structures with a polymer having a low refractive index. It is true that some degree of darkening effect can be obtained by these techniques. For example, when looking at the value of L, which is an index of color density for black fabric, =
15, or it is possible to make L'=14 using this method. However, even if you increase the amount of resin deposited in an attempt to roughly increase the color density, the resin does not adhere uniformly to the surface of the single fibers, and the resin adheres only to the spaces between the fibers, resulting in no increase in the color density.

Other performance, such as reduced adhesion with interlining, discoloration due to wear, discoloration due to dry cleaning, change in texture,
Problems such as staining and color change due to dye bleed-out occurred, and there was a limit to the improvement of color depth.

In addition, there is a method known in Japanese Patent Publication No. 35309/1986 in which a polymer with a low refractive index is uniformly attached to the surface of single fibers rather than to the interfiber voids to increase the color density. It is effective as a technique to uniformly adhere resin to the surface of single fibers existing on the surface of an object. According to this method, it is experimentally possible to reduce L' = 15 to 1 or less. Although this is not possible, it is an effective method for increasing the dark color effect.

However, even with this method, if the color density is lower than 13.5 to 14.0 in L, the discoloration (frosting) due to fringing will be significant (and the change in texture will also be large).

The practical range is L' = 13.5 to 1.
It was in the range of 4.0.

(Problems to be Solved by the Invention) The present invention provides a color deepening technology that can reach an L* value of 11 to 13 without the various consumption performance problems of the prior art described above. That is.

A difference of 0.3 in the ΔL value is dark to the naked eye.

This means that it is possible to determine whether the image is light or not. Therefore, ΔL0 is 0.5 to 2.0% lower than that obtained with conventional practical technology.
The present invention, which can obtain colors as low as 5, can truly be said to be the ultimate deep coloring technology.

(Means for solving problems) That is, the present invention.

r 1) The dyed fiber structure is coated with a resin, and the resin is coated with a film-forming resin (Al and/or inorganic fine particles (
Bl and a low refractive index polymer (C) with a refractive index of 1.55 or less
Further, a thin film of a fluorine compound +1)l is formed on at least one side of the thin film, and 0.2≦α=
It is characterized by satisfying F10≦1.8! a fiber structure.

However, α refers to X-ray photoelectron spectroscopy (X-ray photoelectron spectroscopy).
t.

electron 8pectroscopy) l
This is the value obtained by dividing the number of fluorine atoms calculated from the peak area of the fluorine FIS measured by the number of carbon Crs atoms similarly measured.

2) The film-forming resin (A) is one selected from polyamide, polyacrylamide, polyurethane, and polyurethane acrylic, and the inorganic fine particles (B) are.

Silica or alumina having an average particle size of 0.1μ or less, and a low refractive index polymer (C
The fiber structure according to claim 1, wherein 1 is a silicone-based or fluorine-based polymer, and the total amount of resin is 0.5% by weight to 96-3% by weight based on the fiber structure.

3) Claim 1 or 2, characterized in that the thin film (D) of the fluorine-based compound is formed by a plasma polymerization method or a discharge grafting method, and the thin film has a thickness of 100 to 2000A. The fiber structure described in Section 1.

4) 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 are applied to the dyed fiber structure at a rate of 0. 5
A method for producing a fibrous structure, which comprises curing the adhesion of 96 to 3% by weight, and forming a thin film of a fluorine-based compound on at least one surface thereof.

5) The film-forming resin (M) is one selected from polyamide, polyacrylamide, polyurethane, and polyurethane acrylic, and the inorganic fine particles (Bl) are colloidal silica or alumina sol having an average particle diameter of 0.1 μ or less. , refractive index X, low refractive index polymer tC of S5 or less
5. The method for producing a fibrous structure according to claim 4, wherein said polymer is silicone-based or fluorine-based polymer.

6 film-forming tree JilI (Al and/or inorganic fine particles (B1) and a low refractive index polymer with a refractive index of 1.55 or less (
6. The method for manufacturing a fibrous structure according to claim 5, wherein C) is resin-processed in two to four times.

7) A fibrous structure according to any one of claims 4 to 6, characterized in that a thin film of a fluorine-based compound is formed by a plasma polymerization method, and the film thickness is 100 to 2000Δ. Production method.

8) A fibrous structure according to any one of claims 4 to 6, characterized in that a thin film of a fluorine-based compound is formed by a discharge grafting method, and the film thickness is 100 to 2000Δ. Production method. ”.

The present invention will be explained in detail below.

The fiber structure in the present invention includes natural fibers, synthetic fibers,
Refers to knitted fabrics, woven fabrics, non-woven fabrics, etc. made of semi-synthetic fibers and recycled fibers. The present invention is particularly effective for polyester fiber structures having poor dark color properties.

The resin on which the fiber structure is coated is a film-forming resin (A).
and/or consists of inorganic fine particles (B) and a low refractive index polymer (C1) with a refractive index of 1.55 or less. That is, (Δ)
and (B) and (C1, or (Bl and (C
1 or (A) and fc).

The film-forming resin (A) plays the role of a binder that binds the inorganic fine particles and low refractive index polymer to the fiber structure, and is less likely to discolor or fade due to washing, dry cleaning, or fading compared to the case without (Δ). It is very effective in combating this, and at the same time it also plays a role in adjusting the texture. In addition, a polymer with a relatively low refractive index is desirable, which is important from the perspective of producing a deep color effect. For example, polyamide, polyacrylamide, polyurethane, polyurethane acrylic, etc. are desirable, but other polymers can also be used as long as they have film-forming properties.

Inorganic fine particles (Bl) may be fine particles with an average particle size of 0.1 μ or less, preferably fine particles with a low refractive index and an average particle size of 0.05 μ or less in order to prevent darkening. Colloidal fine particles For example, colloidal silica, alumina sol, etc. are used because they have good dispersibility and do not aggregate.

Inorganic fine particles (Bl are combined with (C), or (A) and (C)
In addition to the mixed system with 1, it may be attached to the fiber structure at once, but it is better to attach inorganic fine particles to the fiber structure in advance and then attach (C) or [A] and (C1). Preferably.In the latter case, the resin component adheres relatively uniformly to the fiber surface using the fine particles as a core, and the resin (A) adheres roughly along the unevenness of the fine particles, and the uneven structure of the resin (Δ) causes the resin component to adhere relatively uniformly to the fiber surface. This is because the chromaticity increases.

A low refractive index polymer with a refractive index of 1.55 or less (C1 is (A
) or (B) is particularly effective when the deep color effect is insufficient in resin processing. Typical polymers include silicone-based or fluorine-based polyesters, dimethyl silicone, amino-modified silicone, or especially Preferably. However, if the weight ratio of the Cl polymer exceeds 80% by weight of the total resin amount, problems may occur such as a change in texture, a decrease in adhesion to the interlining, and dry cleaning resistance, so it is desirable to keep it below 80% by weight. .

Further, 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 effect of deep coloring after resin processing will be small, and in order to give the final product a sufficient degree of deep color, it will take too much time to form a thin film, making it uneconomical. On the other hand, if it exceeds 3% by weight, it is not preferable from the viewpoint of texture. This resin processing method can be any ordinary resin processing method, but the dip and nip method is preferred because it is simple.

Roughly the above (Al component and/or fBl component and (
When mixing components C) and depositing them in a bath, a combination is required that does not damage the dispersion state of the mixed system, and there are restrictions on the components that can be used as (A), (B), and (C1). This may occur as mentioned above.

For example, a multi-stage treatment in which (Bl is deposited first and then (Al and fU) is deposited is desirable. This multi-stage treatment is also important from the point of view of uniformly depositing the resin on the fiber surface. 2 to 4 times. If it is applied separately, the color density improves each time, but even if it is applied five times or more, the effect is small.The color density after this resin processing is L value before resin processing =
15, O (L value -13,5 to 14 for black fabrics)
．． It is desirable that the process be performed to reduce the amount to about 0. Of course there is an antistatic agent in the resin.

It may also contain commonly used agents such as penetrants, antifoaming agents, crosslinking agents, and silane coupling agents.

A thin film layer of a fluorine compound is formed on both or one side of this resin-treated fiber structure. Whether to apply a thin film on one side or both sides should be selected depending on the product, and even if the thin film is applied only on one side, the color can be sufficiently deepened and there is no problem in practical use.

When a thin film layer of a fluorine compound is formed by low-temperature plasma polymerization, the fluorine compound introduced into the system during polymerization under low-temperature plasma is excited and decomposed into various states, causing the polymerization reaction to take place. to form a main chain, a branched structure, or a cross-linked structure. Fluorine elimination is thought to play a very important role in these reactions.

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

The sound of the present invention is produced using X-ray photoelectron spectroscopy (X-ray photoelectron spectroscopy).
.

As a result of examining various thin films through analysis using electron 8peotroscopy (hereinafter abbreviated as XP8), it was found that fluorine-based polymers with a ratio of 0.2≦α≦1.8 are the most effective in terms of deep color effect. . Here, α is the fluorine FIS measured by XP8.
It is the value obtained by dividing the number of fluorine atoms calculated from the peak area by the number of carbon CIS atoms measured in the same manner. α<0.2
In this case, the atomic ratio of fluorine to carbon is too small, which tends to result in a polymer with a high refractive index, resulting in little dark color effect. α〉1
．． In the case of No. 8, the polymer becomes less charged and it is very difficult to lower the frictional charging voltage, and the adhesion to the interlining also decreases.

Methods for forming a thin film are not limited to plasma polymerization, but include so-called resin processing methods and electrical discharge grafting methods. From the viewpoint of effectively forming a thin film on the fiber surface, plasma polymerization methods and electrical discharge grafting methods are effective.

Motsumar, a fluorine-based compound used in the plasma polymerization method, is 02F4. CnHmClp represented by U3F6
F2n -m -p type (n≧2.m20%p≧O1
2n-m-p≧1 integer), CF4.02F6, (:
CnHmOJpBrqE'2n+2 represented by 3Fs
m p q type (n≧11m≧0, p≧0.
9≧o, zn+z −m−p−q≧1 W)
, CnmnCJ'pF2H represented by C<Fs
-m-p cyclic type (n≧3.1n≧o, p≧0,2
n-m-p; an integer of i=1), Onmn (X?pF2n-2-m-p, an integer of .2 It
-2-m - an integer of p≧1), C5FsO is a representative type, Nk'3, 8 is '6, WF6 is a representative type.
There are various types such as sign type.

Among these, those that have a high film formation rate and are industrially preferable are C, Ni'4, Yama F6, (j3FB, 04F8
, 03F60゜02M41?2, etc., but transportation safety 1. Roughly preferred from the viewpoint of film formation speed, etc. 03
F6, Od', 03E60.

Furthermore, some of the stiff fluorine-based compounds have low film-forming ability when used alone, but when mixed with a small amount of hydrogen gas or non-polymerizable gas and subjected to plasma polymerization, the film-forming rate can be significantly improved. C24, c2h, (33F8,
UzM4F2 is a typical example, and the film formation rate can be improved by mixing with a non-polymerizable gas.

Typical examples are 02F (jaFs, 04F, C31"60, etc.).

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

The fluorine-based compound used in the discharge grafting method is preferably a compound having a carbon-carbon double bond and a fluorine atom, such as UnklrnU6pF zn-m-, which is represented by 02E4.03F6. p type (n≧2, m≧0, p≧0.zn-m-p≧1 integer), 2, n=integer from 1 to 4, III: Hor U
H3, B2: MOrF), etc.

Plasma polymerization as used in the present invention refers to a polymerization method that utilizes low-temperature plasma discharge, and refers to a case in which one or more types of 7-mer are supplied during discharge and one-stage polymerization is carried out in the presence or absence of a non-polymerizable gas. To tell.

In addition, the discharge grafting method involves generating radicals by subjecting a resin-processed fiber structure to a low-temperature plasma discharge in the presence of a non-polymerizing gas, in an atmosphere containing one or more polymerizable polymers without exposing it to too much oxygen. or when the resin-treated fiber structure is subjected to low-temperature plasma discharge in the presence of oxygen gas or non-polymerizable gas, the sarashi radicals are converted into peroxides in an oxygen-containing atmosphere, and one or more types of This includes the peroxide method, etc., where the polymer is introduced into an atmosphere containing a polymerizable monomer and polymerized.

Low-temperature plasma is characterized by an average electron energy of 10 eV (10' to 10' K) and an electron density of 109 to 12' crn, which is generated during discharge, and at the same time the electron temperature and gas temperature are It is also called non-equilibrium plasma because no equilibrium is established during the discharge.Electrons, ions, atoms, molecules, etc. are mixed in the plasma that is not generated in the discharge.

Any frequency power source can be used to apply the electric current. In terms of continuity and uniformity of discharge, I Ktiz
~10 Gelz is desirable. In addition, in terms of plasma uniformity in the width direction of the electrode, it is preferable to use 2 to 1 plate per plate, and 1 plate to 1 plate.
When the frequency exceeds 144 Hz and the length of the electrode exceeds 1 rrL, processing spots tend to occur in the length direction. Also 100 Hz
In the following cases, the edge effect of the electrode is likely to occur, and arc discharge is likely to occur at the edge. In addition, the current is alternating current, direct current,
Biased alternating current, pulse waves, etc. can be used. There are two types of electrodes: internal electrodes, which are placed inside the vacuum system, and external electrodes, which are placed outside the polar vacuum system.However, with external electrodes, when the equipment becomes larger, plasma moves particularly to the surface of the workpiece. The treatment effect is low because the plasma loses its activity in the dark and the plasma is scattered and the plasma concentration is diluted. Since the unidirectional electrode method allows the installation of an air elm near the object to be treated, the processing effect is greater than that of the external electrode method.

The electrode shape can be symmetrical or asymmetrical. Symmetrical fl! Poles have more disadvantages. For example, it is almost impossible to flow gas uniformly between large electrodes, and the electric field tends to become erratic at the ends of the roughly large electrodes, which tends to cause processing spots. Therefore, in the case of large plasma processing equipment, asymmetric lI! Poles are preferred. The object to be processed may be set and moved at any position between the electrodes, or may be in contact with one of the electrodes, resulting in less wrinkles and a greater processing effect.

The shape of the electrode on the side that does not come in contact with the object to be processed can be arbitrarily selected, such as a cylindrical one or a rod-shaped one with a polygonal cross section with an acute angle, and the processing effect will also vary depending on the number of electrodes. If it is too small, the processing effect will be small. The shape is preferably cylindrical. In addition, the shape of the electrode on the side that may come into contact with the object to be treated can be drum-shaped, plate-shaped, or deformed. The combinations are not limited to these either.

Further, the material used for 1llatll is metal such as stainless steel, copper, iron, aluminum, etc., and may be coated with glass, ceramics, etc. as required. Of course these il! The electrode may be a water-cooled cooler, and the cooling temperature is appropriately selected depending on the object to be treated.

It is desirable that the cooling water be water with as few impurities as possible, but
This is not particularly the case when electrical leakage due to these impurities is not a serious problem.

Next, the gas to be introduced into the vacuum system should be introduced as far away as possible from the exhaust port of the vacuum pump, and distributed as necessary.Also, it may be introduced between the electrodes. This is important in terms of avoiding gas short baths in the vacuum system, and is also important in order to prevent processing spots from occurring on the object to be processed.

The gas containing a hexamer introduced into the vacuum system may be any of a hexamer gas, a monomer gas and a non-polymerizable gas, or a monomer gas and a polymerizable gas. The gas in the pot may be either gaseous or liquid at room temperature.

The mixture of the non-polymerizable gas or the polymerizable gas and the 7-mer gas can be arbitrarily selected depending on the reactivity of the 7-mer gas, the performance of the formed thin film, etc. The 7-mer gas and the 7-mer gas and other gases can be introduced into the vacuum system separately and mixed within the system, or mixed in advance.
There is no problem in introducing them at the same time, and it is also possible to introduce the seven gases under discharge with a non-polymerizable gas.

The degree of vacuum for generating low-temperature plasma is 1, usually 0.0.
0.01 to 50 Torr is used, but according to the study results of the present inventors, 0.01 to 50 Torr is preferable.

When the degree of vacuum becomes 0.01 Torr or less, the mean free path of ions and electrons becomes large, and the energy of accelerated particles increases, or the total number of accelerated particles that reach the object to be processed is small, and the processing efficiency becomes somewhat low. Moreover, in order to maintain the temperature at 0.01 Torr or less while introducing gas into a large processing chamber, a vacuum pump with a very large displacement is required, which is not desirable in terms of equipment cost. Vacuum level: 5 T
When the value exceeds orr, the mean free path of ions, electrons, etc. becomes small, the energy of accelerated particles becomes small, and the processing efficiency becomes low even though the total number of accelerated particles is large.

The relative position of the fibrous structure disposed between the electrodes has already been described above, but generally the processing efficiency is good if the fibrous structure is disposed in contact with one of the electrodes. Also, if you do not want to apply too much tension to the structure, or if you want to add wrinkles to the structure.
If not, it is desirable to use a type that allows the structure and the w1 stroke to move together, such as one in which the structure is placed in contact with a drum electrode and the structure is moved while rotating the drum. In fact, minute wrinkles often cause processing spots. If there is no need to pay much attention to tension or wrinkles, the structure may be disposed in contact with the plate electrode, and the structure may be moved by sliding over the electrode. Of course, after single-sided treatment, double-sided treatment becomes possible by passing through a place where the electrodes are arranged inversely to the structure. In normal cases, the processing effect on only one side is often sufficient, so this type is preferable from the viewpoint of processing efficiency. However, if it is desired to obtain the effect of treating both sides with only one pair of electrodes, a fibrous structure may be placed between the two electrodes, and the structure may be moved. In this case, the processing effect is generally smaller than when it is placed in contact with the electrode.

Next, from the viewpoint of uniformity of treatment, it is necessary to hold both electrodes parallel to each other, and moreover, they must be arranged at right angles to the traveling direction of the fibrous structure material to be treated. If this condition is not satisfied, processing unevenness will occur in the width direction of the structure.

Roughly speaking, the width of the picture electrode needs to 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 end of the electrode.

If the length is less than 5c1n, the treatment effect will be different in the width direction of the structure, especially in comparison with both sides or near the center, which is not preferable.

The device continuously moves fibrous structures in the atmosphere into a vacuum system, and in some cases the fibrous structures are placed in a pre-vacuum system and can be moved to the processing chamber. It may be a structure in which the structure is partitioned and arranged, or in other words, a structure in which the structure is fibrous or continuously movable. The plasma output is preferably 0.1 to 5 watts/cd as the output acting on the discharge portion. in this case,
The discharge area is the area of the fibrous structure present in the discharge area.

Or, if you divide the value of the plasma discharge part output by the surface area of either electrode, which value is 0.1 to 5 watts/
clI! Nani 1 is good. The output of the discharge section is the voltage of the discharge section, 1
It can be easily calculated by measuring the flow, or as a guide, it may be considered to be 30 to 70% of the output of the plasma 1IIL source. When the plasma output is less than 0.1 W/h/d, the processing takes time and the thickness of the thin film is not sufficient. When the plasma output exceeds 5 W)/d, the discharge becomes somewhat unstable and etching is likely to occur in addition to monopolymerization. In terms of long-term discharge stability of fluorine-based plasma polymerization and discharge grafting, the most preferable range is 0.1 watt/d or more and 2 watts/d or less.

The processing time is preferably about 5 to 600 seconds, but is not necessarily limited to this range. If the treatment time is less than 5 seconds, the thickness of the polymer film will be slightly low, and if the treatment time exceeds 600 seconds, the film thickness of the polymer film will be sufficient, but it may become colored, the surface will become slightly hard, or it will become brittle, which may affect the original performance of the fiber. Unlike (sometimes).

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 potential of the electrode in contact with the sheet-like structure and the potential of the can body (because it is grounded, the earth potential is different, the can body does not act as an electrode, and the discharge is mainly between the two electrodes. Therefore, the plasma acts on the fiber structure without being effectively diluted, and the treatment effect is significantly improved.At the same time, the treatment effect is significantly greater (with less radiation power) compared to the conventional grounding method (in a short time). Since a predetermined effect can be obtained through this process, the device can be made smaller, or in other words, the equipment cost can be reduced, and the running cost can also be reduced to a fraction of the original since the discharge power is reduced.

The thickness of the thin film is preferably 100-2000A. The film does not necessarily have to be in the form of a uniform film (it may be in the form of dots or blocks).The degree of color deepening increases as the film thickness increases, but to obtain the highest degree of darkening,
or more preferable. If it is less than 100A, there is little effect on improving the color density (and if it exceeds 2,000A, the texture tends to be a little hard, and the frosting (cosmetic discoloration) property is poor.
A is most preferred. Also, 300 to 100 OA is most preferable from the viewpoint of improving dye transfer/sublimation prevention properties, water repellency, and dry heat and wet heat abrasion fastness. To measure the film thickness, place the polyester film in a plasma polymerization atmosphere.
A cover glass was placed on top of the sample and processed, and then the cover glass was removed, and the difference in level was measured using a multiple interference microscope or an electron microscope. Further, in the case of discharge graft polymerization, the film thickness in the case of dot-like or block-like polymerization carried out according to this method can also be referred to as the height of the dot-like or block-like protrusions.

As mentioned above, when a thin film is polymerized under low-temperature plasma, the fluorine compounds introduced into the system are excited and decomposed into various states, causing a polymerization reaction and forming a main chain. or form branched or cross-linked structures. It is thought that elimination of fluorine plays a very important role in these reactions.

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

Synthesized from fluorine compound monomer under low temperature plasma
It is easily presumed that such thin films always contain oxygen. This phenomenon is an important factor in maintaining and improving adhesion.

According to XP8 analysis, a small R film with α=F/C, that is,
If a large amount of fluorine is eliminated, crosslinking and branching progress, and at the same time, a large amount of activated carbon remains, which reacts with oxygen inside and outside the system, increasing the oxygen content.

The equipment used to measure the N/C ratio by X-ray photoelectron spectroscopy, which is roughly equivalent to XP8% or ESUa, was a Shimadzu E8CA750, and an E8 FAC-
100 was used.

A thin film formed on a polyester film was punched out to a diameter of 6 m and attached to a sample stand using double-sided tape for analysis. The radiation source is MgKa line (1253,6e
V), and the degree of vacuum in the apparatus was set to 10-7 Torr.

The measurement was performed on the (jts, F engineering s peak) and each peak was
Based on the correction method using d, the correction analysis is performed using () to determine the area of each peak. The obtained area is 1 for Uxs.
00.1''15 is multiplied by the relative intensity of 4.26, and the surface (fluorine/carbon, oxygen/carbon) atomic ratio is directly calculated from the area.

Charge correction is performed using A14 f 7/ of the gold vapor deposited film on the sample.
2 spectra (83,8 eV) as a reference.

By passing the thin film polymerization degree sample through an aqueous solution,
Although the reason is not clear, the toothing property can be significantly improved. It is also possible to roughly improve the frosting properties by adding a softener, an antistatic agent, a penetrating agent, etc. to adjust the texture to the aqueous solution.

Hitherto, attempts have not generally been made to directly attach a fluororesin finishing agent to a fiber structure to increase the darkening effect. This is because if a fluorine-containing coloring agent is attached as the color density is increased, the antistatic performance will be significantly impaired and the adhesion of flakes will increase significantly, making it unusable.

However, in the case of a thin film like the one of the present invention, sufficient antistatic properties can be obtained by slightly increasing the amount of antistatic agent during resin processing.

Furthermore, the present invention is directed to the so-called ``coated fabric''.
A polymer film of a fluorine compound is formed on the surface of the coated fabric to prevent migration and sublimation of the monodisperse dye of the fibers constituting the coated fabric (JP-A-61-186578, JP-A-62-45784). Different techniques.

The coating resin layer in the coated fabric is a relatively thick resin layer made of acrylic, polyurethane, rubber, vinyl chloride, etc., which has waterproofness, air permeability, and moisture permeability. A case that is attached using a coating method, dip method, or nip method to cover or fill the voids in the fabric with a resin layer.The resin layer has micropores to increase water resistance and maintain moisture permeability. In many cases, a thick resin layer is placed on the fiber structure, and at this stage there is almost no effect of deepening the color of the fabrit, and a thin film of fluorine-based compound is applied to the fabrit. Even if it is formed, as described in the prior art section at the beginning. The same level of color deepening effect as that achieved by thin film polymerization alone can be obtained.

As mentioned above, in the present invention, L is made to be 13.5 to 14.0 at the stage of resin-processed fiber structure, and a polymer film of fluororesin is formed on this, so that L is 13.5 to 14.0.
1 to 13, and for this purpose, the amount of resin applied on the fiber structure is small, less than 3% by weight (therefore, it is difficult for the resin to cover or fill the voids in the fiber structure). It is a type of fabric that allows it to be placed uniformly on the surface of single fibers without being coated, and therefore requires a specific combination of components, and is already different from the so-called coated fabric at the stage of being processed with resin. It is.

In this way, the present invention applies resin processing two or more times to uniformly apply resin processing to the fiber surface, and by forming a thin film with a specific structure on the surface of the fiber structure, extremely high dark color property can be achieved. , fiber structures with good dye migration and sublimation resistance, water repellency, and adhesion.

This has been made possible without any problems in terms of consumption performance.

(Example) A description will be given below based on an example.

The color density was evaluated using a Hitachi spectrophotometer 303 using L''a9.

Dye transfer prevention property was measured by closely contacting the plasma polymerized surface of the sample with a white resin-treated cloth of the same type as the sample, immersing it in water, taking it out, blocking excess water with a paper towel, and inserting it between stainless steel plates to obtain a test sample of 100 g/cIN. The sample was placed in an atmosphere at 120° C. for 80 minutes under a load of 120° C., and the degree of contamination on the white background was determined on a gray scale.

Water repellency was evaluated using J18 L-1092 (spray method). Frosting has dry rub fastness (JI8L-0
849) The grade was determined based on the change in concentration of the subsequent sample.

Adhesiveness was determined by adhering to interlining and measuring peeling strength.

The adhesion was carried out by overlapping the sample and interlining and heat-treating them at 150° C. (30 seconds) and a load of 170 y/cd. The peeling method was performed according to JI8 L-1086.

Example! Created a formal black back satin Amundsen fabric made of hollyester structured yarn.

Processed using conventional methods and dyed black. The color depth of this fabric was L'=15.0.

This fabric was treated twice with resin from Kao Corporation.

The first treatment was Schwatt A-10 and Schwatt N-
The fabric was dipped and nipped in an aqueous solution of 20 (crosslinking agent) adjusted to a concentration of n10%, o, and oi%, respectively, and dried using a cylinder dryer and a pin tenter.The second treatment was performed using the fabric. Schwatt TR-420 (urethane acrylic (A) with silicone (U) added)
, Schwara 1-N-20 (crosslinking agent), Electrostripper 'I'A-267 (antistatic agent)
496.0.296.Dip in a solution adjusted to a concentration of 1.0% and adjusted to pH 5 with acetic acid.

It was processed using a nip method and dried using a cylinder dryer and a long loop dryer. The color density of this fabric is 1. *=
It was 13.8. Resin adhesion amount after two treatments is 1.5
% by weight.

This fabric was subjected to low temperature plasma polymerization using CaFsO monomer. The plasma polymerization equipment has a power frequency of 200Ulz
The electrodes consist of a rod-shaped electrode and a drum-shaped electrode, and both the picture electrode and the non-grounded 'fIt electrode are insulated from the can body (grounded). The inside of the can is heated to 5 x 10''2 Torr using a vacuum pump.
Pull it with r f and flow 03F60 gas to 0.2 Tor.
I made it r. 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 rice of the fabrics treated at each treatment time.

As the film thickness increases, the color becomes darker and the water repellency also improves.

It can also be seen that the adhesiveness is also improved compared to after resin processing. The darkened structure of Kohori et al. showed no change in color after dry cleaning, had sufficient chargeability, and had good frosting.

In experiment Nα3, the film thickness was less than Zooμ and there was little darkening effect.
Na 10 had a sufficient dark coloring effect, but the texture was a little hard. As a comparative example, a black dyed peritectic treated with plasma polymerization for 120 seconds had a L value of 13.8, which was comparable to the color obtained only by resin treatment. Also, those processed for 180 seconds are L-13.
, 5, but the discoloration was significant due to wear and tear, and it was not suitable for use as clothing.

Margin under varnish Table 1 Table 2 Example 2 After making a fabric from polyester fibers to which 3% by weight of colloidal silica with an average particle size of 45% was added, the weight loss was 23% by weight.
A crebondigi ossette fabric made of the roughened fibers was produced and dyed black by conventional processing.

A solution was adjusted so that 0.3% by weight of colloidal silica (B) with an average particle size of about 15 and a penetrant were deposited on this fabric,
Depth, nip and dry. 1.5% by weight of a mixture of polyurethane acrylic (Al, dimethyl silicone (0), silane coupling agent, antistatic agent, crosslinking agent, and antifoaming agent) was applied to the fabric, squeezed, and dried using a pin tenter. It was set at 170°C.

Next, plasma polymerization was carried out using the same apparatus as in Example 1 using a 7-mer 03F6 while changing the treatment time in the same manner. Roughly apply silicone softener 0.1 to the fabric of Experiment Magneto 18.
% in water and dried by nipping. kot”b is Nα
The results are summarized in Table 2 as 21.Nα22 is a grounded type in which the drum electrode of the plasma polymerization device is set to the same potential as the can body.
18ii. As the processing time increases, the film thickness increases and the color density improves. When the film thickness was 100A or less in experiment k13, there was little improvement in deep color and water repellency. The film thickness of 2200A in the experiment Nα20 showed little change in texture, but the discoloration due to frosting was grade 2-3, which was somewhat poor. The reliability of Na21, a wet processed product of Nα18, is Nα.
Same as 18, but the frosting was improved. Furthermore, the adhesion, which had significantly decreased due to resin processing, was improved by the plasma polymerized film. It can be seen that Fish 22 is either plasma polymerized by the grounded WL electrode, or its film forming ability is poor compared to Nα17.

Example 3 A Kasitos fabric for school uniforms made of a 50150 blend of polyester and wool was prepared and dyed black using a conventional process.

Silica (B) having an average particle size of 0.1μ was added to this fabric.
) and 7mino-modified silicone (01 in a solid content ratio of 273), a solution containing an antistatic agent was applied to the sieves, nipped, dried at 120°C, heat cured at 160°C, and the solid content was 1. The amount was 2% by weight.

Next, in the same manner as in Example 2, 10% of CaFe monomer was added.
Plasma polymerization was carried out for 17 Fm after adjusting the vacuum to 0.4 Torr. In addition, the black dyed resin-treated fabric was irradiated for 60 seconds using the same plasma discharge device used in Example 2 with argon gas at 201/min and a vacuum level of 0.5 Torr. The discharge grafting was carried out at a vacuum level of 0.4 Torr and a distance of 10 b.

Table 3 below shows the case of plasma polymerized thin film in experiments Nα25 to 29.
In addition, the case of the discharge graft thin film is shown in Experiments Nα31 to Nα34.

The products according to the present invention were excellent in deep color effect, had a quality that could withstand practical use in other consumption performance, and had sufficient dry cleaning resistance.

For comparison, a sample after black dyeing was irradiated with argon.
Experiment Nα35 shows a sample subjected to discharge grafting treatment for 240 seconds with 'g monomer, but the dark color effect ratio was 13.5 and the frosting property was 2nd grade, which was not suitable for practical use.

Claims (1)

[Scope of Claims] 1) A dyed fiber structure is coated with a resin, and the resin is coated with a film-forming resin (A) and/or inorganic fine particles (B).
) and a low refractive index polymer (C) with a refractive index of 1.55 or less, and a thin film (D) of a fluorine-based compound is formed on at least one side of the polymer (C), and the thin film has a diameter of 0.2≦α=F/
A fiber structure that satisfies C≦1.8. However, α refers to X-ray photoelectron spectroscopy (X-rayPhotoelectron spectroscopy).
It is the value obtained by dividing the number of fluorine atoms calculated from the peak area of fluorine F_I_S measured by electron spectroscopy) by the number of carbon C_I_S atoms measured in the same manner. 2) The film-forming resin (A) is one selected from polyamide, polyacrylamide, polyurethane, and polyurethane acrylic, and the inorganic fine particles (B) are silica or alumina having an average particle diameter of 0.1 μ or less. , a patent claim in which the low refractive index polymer (C) with a refractive index of 1.55 or less is a silicone-based or fluorine-based polymer, and the total resin amount is 0.5% to 3% by weight based on the fiber structure. The fibrous structure according to item 1. 3) Claim 1 or 2, characterized in that the thin film (D) of the fluorine-based compound is formed by a plasma polymerization method or a discharge grafting method, and has a thickness of 100 to 2000 Å. The fiber structure described in Section 1. 4) 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 are applied to the dyed fiber structure at zero ．．
A method for producing a fibrous structure, which comprises curing 5% to 3% by weight of the fibrous structure and forming a thin film of a fluorine compound on at least one surface thereof. 5) The film-forming resin (A) is one selected from polyamide, polyacrylamide, polyurethane, and polyurethane acrylic, and the inorganic fine particles (B) are colloidal silica or alumina sol having an average particle diameter of 0.1 μ or less. , low refractive index polymer (C) with a refractive index of 1.55 or less
5. The method for manufacturing a fibrous structure according to claim 4, wherein the fibrous structure is a silicone-based or fluorine-based polymer. 6) 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 are resin-processed in two to four times. Method of manufacturing structures. 7) The fibrous structure according to any one of claims 4 to 6, characterized in that the thin film of the fluorine-based compound is formed by a plasma polymerization method and has a thickness of 100 to 2000 Å. manufacturing method. 8) A fibrous structure according to any one of claims 4 to 6, characterized in that a thin film of a fluorine-based compound is formed by a discharge grafting method, and the film thickness is 100 to 2000 Å. Production method.