JPH0529716B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Field of Application> The present invention relates to a resin-processed product of a polyester fiber structure that is excellent in preventing migration and sublimation of disperse dyes, and a method for producing the same. <Prior art> When dyeing polyester fiber structures with disperse dyes, the darker the color and the smaller the molecular weight of the dye, the easier it is for the dye to migrate to the fiber surface, resulting in less friction when dry or wet. fastness,
Sublimation fastness has decreased, and staining and discoloration have become problems. In addition, in the case of dyed products treated with resins such as urethane, acrylic, and vinyl chloride, the dye is highly compatible with the resin, so it dissolves into the resin over time and becomes colored, causing the resin-processed product to become colored. This creates problems of migration and contamination. For example, Japanese Patent Application Laid-Open No. 59-82469 discloses a method for preventing migration contamination of resin-processed products. This method involves forming a crosslinked film on the dyed material using a melamine resin, and involves the following steps: resin application, drying, and heat curing. The process is complicated, and it changes the texture of the product. Tokukai Akira
No. 59-82469 does not introduce the concept of SP value as in the present invention.In fact, the SP value of common melamine resins is 8.0 to 9.8, which is higher than that of common disperse dyes.
It is similar to the SP value. The present invention is fundamentally different from JP-A-59-82469 in its approach to transitional sublimation, and its effects are incomparably superior. In addition, JP-A-59-106588 describes that after treating the dyed material with a finishing agent, it is treated with low-temperature plasma to increase the abrasion fastness and the washing durability of the finishing agent, but the improvement effect of this method is The process is complicated. In addition, in JP-A-53-16085 and JP-A-53-8669, in order to prevent the elution of plasticizers contained in polyvinyl chloride resin, gaseous fluorocarbons and gaseous organosilicon compounds are added. It is mentioned that the surface is coated with a dense polymer upon contact with a gas plasma. As described above, the technology of forming a plasma polymerized film on the surface of PVC using a plasma polymerization method using low-temperature plasma discharge to prevent the elution of plasticizers has been known, but the present inventors have We introduced the concept of SP value for the first time to prevent migration and sublimation of dyes, and discovered a sheet-like structure that has an extremely excellent prevention effect using plasma polymerization and other methods, and a method for producing the same. That is, the present inventors formed a thin film on a polyester fiber structure dyed with a disperse dye by a plasma polymerization method using low-temperature plasma discharge in a gas containing a monomer having a difference of 0.5 or more from the disperse dye. Later, by processing it with resin, they succeeded in manufacturing a resin-processed product that was excellent in preventing the migration and sublimation of disperse dyes. Furthermore, the present inventors have discovered for the first time that these polymeric films are effective in preventing sublimation transfer of fractional dyes to resin processing layers. <Problems to be Solved by the Invention> As a result of many years of detailed research into prevention of dye sublimation migration in resin processed products of polyester fiber structures dyed with disperse dyes, the present inventors have found that polyester fiber structures and It has been found that forming a thin film between the resin processing layers is effective. As a result of more detailed investigation, they discovered that the monomer or polymer capable of forming a thin film is effective only when it has a specific SP value for disperse dyes. Furthermore, the method for forming the thin film may be conventionally known polymer coating or lamination, or plasma polymerization using low-temperature plasma discharge. That is, the present invention aims to provide a sheet-like structure that prevents the migration and sublimation of disperse dyes, has a simple process, does not change the texture of the product, and is sufficiently durable. Between the resin processing layers,
The above objective is achieved by providing a thin film with a thickness of 100 to 10,000 Å formed from a monomer or polymer having an SP value different from that of the disperse dye by 0.5 or more. <Means for Solving the Problems> The present invention provides a method of applying polyester fibers dyed with a disperse dye to a surface layer of at least one side of a fiber structure containing 10% by weight or more of polyester fibers with a film thickness of 100 to 10,000 Å. A thin film layer consisting of a monomer or polymer of a fluorine-containing compound or a silicon-containing compound having the following solubility parameter - SP value [(cal/cm ³ ) ^1/2 ] is formed, and at least one side of the thin film layer is Sheet-like structure whose surface is coated with a resin layer |Asp−Bsp|≧0.5 (However, Asp is the SP value of a monomer or polymer of a fluorine-containing compound or a silicon-containing compound,
Bsp is the SP value of the disperse dye. ), and a monomer of a fluorine-containing compound or a silicon-containing compound having an SP value represented by the above formula is added to the surface layer of at least one side of a fiber structure containing 10% by weight or more of polyester fibers dyed with a disperse dye. This method of manufacturing a sheet-like structure is characterized by forming a thin film layer of 100 to 10,000 Å in thickness and further forming a resin layer on at least one surface of the thin film layer. The fibrous structure referred to in the present invention refers to knitted and woven fabrics, nonwoven fabrics, etc., and naturally also includes those subjected to primary antistatic processing, water repellent processing, water absorption processing, etc. Disperse dyes are S, D, C and A, A, T,
C, C, refers to dyes that belong to the co-edited color index as disperse dyes, including azo-based, anthraquinone-based, quinoline-based, quinone-based, phthalon-based, etc.; May be used. The polyester referred to in the present invention refers to aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, phthalic acid,
Synthesized from aliphatic dicarboxylic acids such as adipic acid and sebacic acid or their esters and diol compounds such as ethylene glycol, diethylene glycol, 1-4-butanediol, neopentyl glycol, and dichlorohexane-1,4-dimethanol. In particular, polyesters in which 80% or more of the repeating structural units are ethylene terephthalate units are preferred. Alternatively, the above polyester component may be copolymerized with polyalkylene glycol, glycerin, pentaerythritol, methoxypolyalkylene glycol, bisphenol A, sulfoisophthalic acid, etc., or a product mixed with a matting agent, a heat stabilizer, a pigment, etc.
Of course, it is not limited to these. Polyester fibers may of course be short fibers or long fibers, and also include conjugates of polyester and other fibers, core-sheath fibers, multicore core-sheath fibers, and the like. In short, it is sufficient that the polyester fibers are dyed with a disperse dye, and any fiber structure containing 10% by weight or more of the fibers is sufficient. Containing 10% or more means mixed weave,
Various methods such as blended spinning, mixed knitting and weaving are possible. At less than 10%, migration and sublimation of disperse dyes does not pose a major problem. The effect of this invention becomes significant at 10% or more. In the present invention, the solubility parameter SP value [(cal/cm ³ )
^1/2 ] is Polymer Handbook-337--
Group Molar described on page 359-339 B ₂ or B ₁
This value is calculated using the formula SP=dΣG/M from the structural formula using Attraction Constants (G), molecular weight (M), and density (d).The SP value calculation results for representative substances are shown below. polyethylene terephthalate (10.7),
Polyurethane (8-10), butyl polyacrylate (8.5-9.5), polyvinyl chloride (9.5), and disperse dye (8.3-9.7). In this way, the SP value of disperse dye is
The SP value is closer to that of polyurethane, polyacrylic acid ester, polyvinyl chloride, etc.
The disperse dye migrates to the resin layer with better compatibility. Monomers or polymers with an SP value that differs by 0.5 or more from the solubility parameter SP value of the dye are defined as the SP value when there is only one type of disperse dye, but
If 15 or more types of disperse dyes are blended, the SP value of each disperse dye multiplied by the blending ratio is taken as the average SP value, and the SP value differs by 0.5 or more from that SP value.
It has an SP value. Of course, if more than one type of disperse dye is blended, each disperse dye
A monomer or polymer with an SP value that is 0.5 or more lower than the lowest SP value among SP values, or an SP that is 0.5 or more higher than the highest SP value of a disperse dye.
If a monomer or polymer having a certain value is used, the effect of preventing migration and sublimation will be even more remarkable. Also, when using a mixture of monomers or polymers, the average BP value is calculated in the same way as the blending of disperse dyes. The monomer or polymer in the present invention consists of a fluorine-containing compound or a silicon-containing compound, such as a gas such as CF ₄ , C ₂ F ₄ , Freon, C ₃ F ₈ , or a fluorinated alkyl acrylate. Examples include solutions, various silane coupling agents, linear polydimethylsiloxanes containing 2 to 11 Si atoms, aliphatic fluorocarbons, aromatic fluorocarbons, Teflon, silicone rubber, and the like. These monomers and polymers may be arbitrarily selected depending on the method of forming a thin film, resin processing, type of disperse dye, each SP value, etc., and may be used alone or in combination of two or more. The thin film layer referred to in the present invention may be formed by coating or laminating a polymer, or may be formed by coating or laminating a polymer.
After applying a monomer or polymer, it may be modified by low-temperature plasma treatment using a non-polymerizable gas, or by low-temperature plasma discharge in a gas containing a monomer. It may also be a plasma polymerized film. In addition, even in a two-step method in which active sites capable of radical polymerization are formed on a fiber structure by low-temperature plasma discharge, and then exposed to a monomer capable of radical polymerization without exposure to oxygen to form a polymer film. good. In addition, after forming active sites capable of radical polymerization by low-temperature plasma discharge, they are exposed to oxygen-containing gas to form a stable peroxide.
It may also be a peroxide method in which a polymer film is formed by treatment in a monomer solution and gas. The method of forming the thin film layer is not particularly limited. By applying a monomer or polymer onto a fibrous structure and then subjecting it to low-temperature plasma treatment, it can be crosslinked and polymerized to form a thin film that has good adhesion to the resin layer. A thin film having a thickness of 100 to 10,000 Å formed by the plasma treatment or plasma polymerization method not only does not impair the texture and appearance, but also improves the water resistance and water repellency of the sheet-like structure. Maintains sufficient moisture permeability and air permeability.
The reason why such a thin film can prevent dye migration and sublimation is because the plasma polymerized film has a uniform thickness and
It tells you whether or not it has spots. In addition, with the conventional method, the adhesion with the resin layer was very poor.
By plasma treatment or plasma polymerization, the adhesion to the resin layer is extremely good. Film thickness is 10000
If it exceeds Å, the texture tends to become a little hard.
When the thickness is less than 100 Å, the film may be damaged due to friction, rubbing, etc., and the effect of preventing migration and sublimation in that area is likely to be impaired. Furthermore, if the film thickness is less than 100 Å, the effect of improving water resistance will be somewhat small. A more preferable film thickness is 500 to 10,000 Å. Further, if this sheet-like material satisfies the formula y>-x+500, it becomes a structure having excellent waterproof and moisture permeable functions with excellent water resistance, water repellency, air permeability, and moisture permeability. Resin processing in the present invention refers to resin processing that is generally performed, and includes a dip nip method, a dipping method, a coating method, and a lamination method on at least one side of a thin film formed on the surface layer of at least one side of a fiber structure. The method is not particularly limited to these methods. In terms of the effects of the present invention, coatings of resins with strong migration sublimation, such as latexes such as polyurethane, polyacrylic esters, polymethacrylic esters, styrene-butadiene rubber, polyvinyl acetate, chlorosulfonated polyethylene, polyvinyl chloride, etc. It is particularly effective for materials and laminates. It is the solubility parameter of disperse dye
This is thought to be because the SP values of these resins are similar. In addition, these resin treatments are not limited to one type of resin, and may be mixed resin treatments or resin treatments that are repeated one or more times.The layer formed from these is called a resin layer, so a resin layer is a multilayer resin layer. Sometimes it becomes. However, in this specification, these are considered more as resin layers. The low-temperature plasma referred to in the present invention is a plasma generated during discharge with an average electron energy of 10 eV (10 ⁴ ~
It is characterized by an electron density of 10 ⁹ to ^{10 12} cm ^-3 (10 ⁵ K) and is also called a non-equilibrium plasma because there is no equilibrium between the electron temperature and the gas temperature. Electrons, ions,
Atoms, molecules, etc. are mixed. Any frequency power source can be used to apply the voltage. From the viewpoint of sustainability and uniformity of discharge, 1 KHz to 10 GHz is desirable. In terms of plasma uniformity in the width direction of the electrode, it is preferably 1 KHz to 1 MHz, and if it is 1 MHz or more and the length of the electrode exceeds 1 m, processing spots are likely to occur in the length direction. Also
Below 100Hz, the edge effect of the electrode tends to occur, and arc discharge tends to occur at the edge. Further, as the current, alternating current, direct current, biased alternating current, pulse waves, etc. can be used. Electrodes can be divided into internal electrode methods, which are placed inside the vacuum system, and external electrode methods, which are placed outside the vacuum system.With the external electrode method, as the equipment becomes larger, plasma moves particularly to the surface of the workpiece. During the process, the activity is lost or the plasma is scattered and the plasma concentration is diluted, resulting in little processing effect. On the other hand, with the internal electrode method, the discharge electrode can be installed near the object to be treated, so the treatment effect is greater than with the external electrode method. Electrode shapes can be divided into symmetrical and asymmetrical. In the case of a large plasma processing apparatus where the processing width of the object to be processed is large and therefore a large electrode is required, symmetrical electrodes have more disadvantages. For example, it is almost impossible to flow gas uniformly between large electrodes.
Furthermore, the electric field may be disturbed at the edge of the larger electrode,
Processing spots are likely to occur. Therefore, it has been found that asymmetric electrodes are preferable for large-scale plasma processing equipment. Although the object to be processed can be set and moved to any position between the electrodes, there are cases where the object is in contact with one of the electrodes, causing 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 from one or more cylindrical ones, or rod-shaped ones with a polygonal cross section with an acute angle, but the processing effect also depends on the number of electrodes. is different, and 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 processed can be drum-shaped, plate-shaped, or modified shapes thereof, but the shape and combination thereof can be used. It is not limited to these.
In addition, metals such as stainless steel, copper, iron, and aluminum can be used for the electrode material, and glass,
It may be coated with ceramics or the like. Of course, these electrodes may be water cooled if necessary.
The cooling temperature is appropriately selected depending on the object to be treated. The cooling water is desirably 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 with a supply port as far away as possible from the exhaust port of the vacuum pump, and distributed as necessary. It may also be introduced between electrodes. This is important in the sense of avoiding short passes of the gas within the vacuum system, and is also important in order to prevent processing spots on the object to be processed. The monomer-containing gas introduced into the vacuum system may be a monomer gas, a monomer gas and a non-polymerizable gas, or a monomer gas and a polymerizable gas. The monomer gas may be either gaseous or liquid at room temperature. The mixing ratio of non-polymerizable gas or polymerizable gas and monomer gas depends on the reactivity of the monomer gas,
It can be arbitrarily selected depending on the performance of the thin film formed. The monomer gas and other gases may be introduced separately into the vacuum system and mixed within the system, or may be mixed in advance and introduced at the same time. A mass gas may also be introduced. The degree of vacuum for generating low-temperature plasma is usually 0.001 to 50 Torr, but according to the results of studies by the present inventors, 0.01 to 5.0 Torr is desirable. When the degree of vacuum is less than 0.01 Torr, the mean free path of ions and electrons increases and the energy of the accelerated particles increases, but the total number of accelerated particles that reach the object to be processed is small, and the processing efficiency becomes somewhat low. Moreover, maintaining a large processing chamber at less than 0.01 Torr while introducing gas requires a vacuum pump with a very large displacement, which is not desirable in terms of equipment cost. When the degree of vacuum exceeds 5.0 Torr, the mean free path of ions, electrons, etc. becomes small, the energy of accelerated particles becomes small, and processing efficiency becomes low even though the total number of accelerated particles is large. Furthermore, although the relative position of the fibrous structure placed between the electrodes has been described above, processing efficiency is generally good if it is placed in contact with one of the electrodes. In addition, if you do not want to apply too much tension to the structure or do not want the structure to wrinkle, place the structure in contact with a type that allows the structure and electrode to move together, such as a drum electrode. , one that moves the structure while rotating the drum is desirable. 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 placed in contact with the plate electrode, and the structure may be moved by sliding on the electrode. Of course, after single-sided treatment, double-sided treatment is possible by passing through a place where the electrode is arranged inversely to the structure. In normal cases, the processing effect on only one side is often sufficient, so this type is desirable from the viewpoint of processing efficiency. However, if you really want to obtain the double-sided treatment effect with just one pair of electrodes, a fiber structure should be placed between the two electrodes.
All you have to do is move the structure. In this case, the processing effect is generally smaller than when it is placed in contact with the electrode. Considering this phenomenon in terms of discharge characteristics, it can be explained by the voltage drop characteristics between the two electrodes. That is, it is said that the voltage drop characteristic between the two electrodes is the largest near the low voltage side electrode, followed by the high voltage side, and the voltage drop near the middle between the two electrodes is small. This voltage drop is proportional to the strength of the electric field, and the larger the voltage drop, the more energy can be given to the charged particles. In the case of a DC system, the low voltage side electrode and high voltage side electrode are easily determined, but
In the case of the AC system, the low voltage side and the high voltage side change over time, so it is not possible to distinguish between the low voltage side electrode and the high voltage side electrode. However, in any case, it is thought that the closer to the electrode the larger the voltage drop and the greater the treatment effect. Next, from the point of view of uniformity of treatment, both electrodes must be held parallel and 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. 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 electric field non-uniformity at the ends of the electrodes. If this length is less than 5 cm, the treatment effect will be different in the width direction of the structure, particularly on both sides, compared to the center area, which is undesirable. In the present invention, the movement of a structure means that
This device can continuously move the fiber structure in the atmosphere into the vacuum system and process it, and the fiber structure can be placed in a pre-vacuum system and be moved to the processing chamber. It refers to those arranged in partitions, but in short, any structure that allows the fiber structure to move continuously may be used. Plasma output is the output acting on the discharge part.
A value of 0.1 to 5 watts/cm ² is desirable. In this case, the area of the discharge part is the area of the fiber structure present in the discharge part, or the value of the output of the plasma discharge part divided by the surface area of either the counter electrode, whichever value is 0.1 to 5 watts/ It should be ^cm2 . The output of the discharge section can be easily calculated by measuring the voltage and current of the discharge section, but one guideline is to calculate the output of the plasma power supply.
It can be considered as 30-70%. When the plasma output is less than 0.1 W/cm ² , the plasma polymerization process takes time and the thickness of the polymerized film is not sufficient. When the plasma output exceeds 5 watts/cm ² , the discharge becomes somewhat unstable and etching is likely to occur in addition to polymerization. The processing time is preferably about 5 to 600 seconds, but is not necessarily limited to this range. When the treatment time was less than 5 seconds, the film thickness of the polymerized film was slightly lower than 600
If the time exceeds seconds, the thickness of the polymer film will be sufficient, but the polymer film may become colored, the surface may become slightly hard, or it may become brittle, which may cause the fiber's original performance to differ. The thickness of the thin film formed by the above method was measured using a multiple interference microscope or an electron microscope. As a result, we used a monomer with an average SP value that was 0.5 or more away from the average SP value of the disperse dye, and
It has been found that a thin film having a film thickness of Å can completely prevent migration and sublimation of the dye.
Even if the film thickness is less than 100 Å, it is effective, but as mentioned above, there is a slight drawback in friction durability. Further, in order to obtain sufficient durability, it is preferable to have a film thickness of 500 Å or more. However, depending on the type of monomer or resin,
Some have sufficient durability at 100 Å. 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 structure and the potential of the can (earth potential because it is grounded) are different, the can does not act as an electrode, and discharge mainly occurs between the two electrodes. . Therefore, the plasma acts on the structure without being diluted, and the treatment effect is significantly higher. At the same time, the treatment effect is significantly higher than that of the conventional grounding method with less discharge power, and the desired effect can be achieved in a short time. As a result, the device can be made smaller, or in other words, the equipment cost can be reduced.Moreover, since less discharge power is required, the running cost can be reduced to about a fraction. A sheet-like structure consisting of at least three layers, which has a thin film obtained by plasma treatment and plasma polymerization between the fiber structure and the resin layer, has the same air permeability and properties that resin-processed fiber structures have. Water resistance and water repellency have been improved without compromising moisture permeability. A detailed explanation will be given below using examples. In addition, water repellency, water pressure resistance, air permeability, and moisture permeability meet JIS L
-1092 (spray method), JIS L-1092 (A method), JIS
The durability was evaluated by measuring according to the L-1096 A method (Fragir method) and JIS Z-0208 method, and washing was performed 10 times according to JIS L-0217-103 method. Regarding transfer sublimation, the plasma-polymerized surface of the sample was brought into close contact with the treated surface of a white resin-treated cloth of the same type as the sample, and the sample was sandwiched between scissors on a stainless steel plate and placed in an atmosphere of 120℃ under a load of 100 g/cm ² for 80 minutes. The degree of contamination on the white background was determined on a gray scale. Measurements were conducted and evaluated in two ways: dry and wet. Various polymers and fibers were obtained by conventional methods, and were dyed and processed into plain woven fabrics. In addition, plasma treatment was performed only on the resin-treated surface of the fiber structure, and the fastness of the treated surface was measured. In Table 1, in Comparative Example 1 and Examples 1 to 19, polyester fabrics were dyed with Paianil Violet 6R.
(BASF) (SP value 9.4).
After applying a thin film using various methods, resin processing was performed. In Example 1, a dyed material was coated with a futsuo-based resin using a coating method, treated with Ar plasma to improve adhesion, and then coated with urethane. In Example 2, FA-8 (Showa Denko) was used for dyeing.

[Formula] was applied by the dip-nip method, treated with Ar plasma, polymerized, and then coated with urethane. In Examples 1 and 2, a thin film was applied by resin processing and then urethane processing, but the SP value of the dye was 9.4, while the SP value of the futsuo-based film was 6.2.
FA-8 has a difference of 0.5 or more from 5.5, and it can be seen that the dye transfer sublimation fastness is greatly improved compared to Comparative Example 1 which does not have a thin film. Examples 3 to 5 are C ₂ F ₄ (PCR Research
This is the result of applying a thin film using plasma polymerization method in Cchemical, INC) gas and examining the effects of processing time and film thickness, but a thin film was not formed with a processing time of 2 seconds, and no improvement in fastness was observed. However, as the processing time increases, the thin film formed also becomes thicker, and its fastness improves significantly. Examples 6 and 7 are the results of applying a thin film by plasma polymerization in a gas mixture of C ₂ F ₄ and Ar at a ratio of 1:1, and then coating with urethane. There is almost no change in film thickness or fastness. This means that even if expensive C ₂ F ₄ is diluted with cheap Ar, it will still be effective.
It has great operational merits and is effective in that monomers are effectively utilized due to the Penning effect of Ar gas. Further, Examples 3 to 7 satisfy y>-x+500 (x: water pressure resistance, y: moisture permeability). Examples 8 and 9 were conducted in a gas containing a mixture of C ₂ F ₄ and CH ₄ at a ratio of 1:1, but the dye transfer sublimation fastness was significantly different from Comparative Example 1. had improved. Examples 10 to 15 are ( _CH3 ) _3SiCl (TMCS, Toray)
Examples 10, 11, and 12 were conducted in gas.
In Examples 13 and 14, the effect of the degree of vacuum, in Examples 13 and 14, the effect of processing time, and in Examples 11 and 15, the effect of processing power was investigated. As the vacuum decreases, as the processing time increases, and as the power increases, the thin film becomes thicker and its fastness improves significantly. Examples 16 to 19 are examples in which TMCS and Ar were mixed in a 1:1 ratio, but the film formation rate was slightly lower due to the introduction of Ar compared to Examples 10 to 15. However, the fastness remains almost the same and is greatly improved compared to Comparative Example 1. However, when the treatment time was 2 seconds and the film thickness was 30 Å, there was no significant difference in fastness from Comparative Example 1. Examples 20-29 are dye Dianix Diazo Black
Polyester fabric dyed with T (Mitsubishi Kasei) (SP value 8.5)

[Formula] (VDEMS, Petrarch Systems Ins.) After processing in gas,
Urethane coated. We also investigated processing in a gas mixed with C ₂ H ₆ . As a result, processing time 2
At a film thickness of 60 to 70 Å, sufficient fastness could not be obtained. There was almost no change due to the introduction of C ₂ H ₆ . Except for Examples 26 and 29, the Examples with a film thickness of 100 Å or more showed greatly improved fastness compared to Comparative Example 2, which did not have a thin film. In Table 2, Examples 30 to 39 are dyes
Sumikaron Diazo Navy 3B (Sumitomo Chemical) (SP value
9.3) Polyester fabric dyed with
Difluorodichloromethane (Freon 12, Tokyo Kasei Kogyo) (SP value 5.5) and Freon 12 and Butadiene
A thin film was applied by plasma polymerization in a -1.3 mixed gas, and then treated with urethane, acrylic, or vinyl chloride resin. Although the thickness of the film decreased as the plasma polymerization treatment time decreased, the transfer sublimation fastness was greatly improved compared to Comparative Example 3, which did not have a thin film, when the film thickness was 100 Å or more. Further, in the treatment in a mixed gas of Freon 12 and polymerizable Butadiene-1, 3, the film formation rate was improved and the fastness was also greatly improved. Even when the resin treatment was acrylic or vinyl chloride coating other than urethane, the transfer sublimation fastness was greatly improved compared to Comparative Examples 3, 4, and 5. Examples 40 and 41 are blended dyes in which dyes with SP values of 8.3 and 9.3 are blended in a 1:1 ratio (SP value: 8.3×0.5+
9.3×0.5=8.8)
After treatment in CH ₂ =CHSi(OCOCH ₃ ) ₃ (VATS, SP value 8.2) and VDEMS gas, urethane resin processing was performed. This shows a significant improvement over Comparative Example 6 which does not have a thin film. VTAS
This shows that the plasma polymerization treatment by VDEMS is less effective than the treatment by VDEMS. This is thought to be due to the presence of dyes with SP values close to VTAS in the blended dyes. However, the blended dye
It has a difference of 0.5 or more from the SP value, and has a sufficiently practical effect of preventing migration and sublimation. In Example 42, after performing low-temperature plasma treatment in Ar gas to form active sites capable of radical polymerization, VDEMS gas was immediately introduced into the system without exposing it to oxygen, and a graft polymerization film was prepared using a two-step method. was formed. Thereafter, urethane coating was applied according to a conventional method. The transfer sublimation fastness of the sample was greatly improved. In Example 43, a peroxide capable of radical polymerization was formed by low-temperature plasma treatment in O ₂ gas, and then dip-nipped in a 20% aqueous solution of VDEMS to apply VDEMS onto the fiber structure,
A graft polymerized film by the peroxide method was formed by heat treatment at 80°C under N ₂ for 30 seconds.
Thereafter, a urethane coating was applied according to a conventional method. This treated fabric had greatly improved migration and sublimation fastness of disperse dyes.

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Scope of Claims] 1. A fiber structure containing 10% by weight or more of polyester fibers dyed with a disperse dye has a film thickness of 100 to 10,000 A on the surface layer of at least one side, and has the following solubility parameter -SP. A thin film layer made of a monomer or polymer of a fluorine-containing compound or a silicon-containing compound having a value [(cal/cm ³ ) ^1/2 ] is formed, and at least one surface of the thin film layer is coated with a resin layer. A sheet-like structure made of ｜A _SP −B _SP ｜≧0.5 (However, A _SP is the SP value of the monomer or polymer of the fluorine-containing compound or silicon-containing compound, and B _SP
is the SP value of the disperse dye. ) 2. A sheet-like structure according to claim 1, wherein the sheet-like structure satisfies the following formula. y>-x+500 (x≧0, y≧0) y; Moisture permeability of sheet-like structure, g/m ² /24h (JIS Z-0208) x; Water pressure resistance of sheet-like structure, mm (JIS L- 1092) 3 The surface layer of at least one side of a fiber structure containing 10% by weight or more of polyester fibers dyed with a disperse dye is coated with monomers or heavy fluorine-containing compounds or silicon-containing compounds having the SP value below. 1. A method for producing a sheet-like structure, comprising forming a thin film layer having a film thickness of 100 to 10,000 A by combining the two, and further forming a resin layer on the surface of the thin film layer on at least one side. ｜A _SP −B _SP ｜≧0.5 (However, A _SP is the SP value of the monomer or polymer of the fluorine-containing compound or silicon-containing compound, and B _SP
is the SP value of the disperse dye. ) 4 A patent claim characterized in that a monomer or polymer of a fluorine-containing compound or a silicon-containing compound is applied to the surface layer of at least one side of the fibrous structure, and then a thin film layer is formed by low-temperature plasma treatment. A method for manufacturing a sheet-like structure according to scope 3. 5. A sheet according to claim 3 or 4, characterized in that a thin film layer is formed by low-temperature plasma polymerization using a monomer-containing gas on the surface layer portion of at least one side of the fibrous structure. A method for manufacturing a shaped structure. 6. The sheet according to claim 4 or 5, wherein the low-temperature plasma treatment or low-temperature plasma polymerization is performed in a low-temperature plasma device having a non-grounded electrode insulated from the can body. A method for manufacturing a shaped structure.