JPS61186578A - Sheet like structure and its production - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION Polyester fiber is a fiber that has excellent advantages such as easy care properties. However, there are very few examples of polyester fibers being used in resin-processed products such as moisture-permeable waterproof fabrics, coated fabrics, and laminated fabrics on the market. The mainstream in this field is fabrics made of nylon fibers. The reason why polyester fibers are not used is that when the above-mentioned resin-processed products are made using polyester fibers, the disperse dye that dyes the polyester migrates through the resin layer, and the dyes are released during storage, sewing, or wearing. This is because contamination occurs. This is thought to be because nylon is dyed with an ionic dye and the nylon and dye are chemically bonded, whereas in the case of polyester, the disperse dye is not chemically bonded.

Furthermore, it has been clarified through studies by the present inventors that the solubility parameter of disperse dyes is lower than that of polyester in resins used for resin processing, such as polyurethane.
It has a solubility parameter close to that of polyacrylic acid ester, polyvinyl chloride, etc., and has good affinity for polyester.
This is thought to be because the affinity for the resin layer is greater.

There have been no attempts to prevent the migration and sublimation of disperse dyes. For example, as disclosed in Japanese Patent Application Laid-open No. 59-82469, a melamine yarn thread is added to a fiber structure and cross-linked by heat to reduce the diffusion rate of the dye, allowing the dye to pass through the layer. However, the melamine thread film hardens the texture of the fiber structure and has poor adhesion between the melamine and the resin layer, and the melamine solubility parameter SP [ The SP value is 8 to 95, which is almost the same as the disperse dye, and the effect of preventing dye migration and sublimation is small.

It is also possible to add silicone emulsion or fluorine emulsion to the fiber structure, but it is difficult to completely cover the fiber surface, has little effect on preventing migration and sublimation, and has extremely poor adhesion with the resin layer. There isn't.

Furthermore, as shown in Japanese Patent Application Laid-Open No. 58-214587, it is possible to form a membrane after processing a fiber structure with a resin, but it is extremely difficult to form a membrane using conventional methods. This is because these resin treatments are mainly solvent-based, and the resin-treated surfaces are generally lipophilic. Therefore, ordinary water-dispersed emulsions are repelled and do not have film-forming properties. Furthermore, even if a solvent-based resin is considered for adhesion to a lipophilic surface, the solvent must not dissolve the already formed resin, and if it does not swell the resin at all, it will not have adhesive properties. Like,
This is because selecting a solvent is extremely difficult. Therefore, a special pretreatment process is required, which complicates the process, and the adhesive strength is also poor.

Still, JP-A-53-16085, JP-A-53-866
No. 9 requires that a gaseous fluorocarbon or gaseous organosilicon compound be brought into contact with an inert gas plasma to coat the surface with a dense polymer in order to prevent the elution of the plasticizer contained in the polyvinyl chloride resin. is stated. As described above, it is known that a plasma polymerized film is formed on the surface of vinyl chloride by a plasma polymerization method using low-temperature plasma discharge, but this technique is limited to a technique for preventing the elution of a plasticizer.

The present inventors introduced the concept of SP value for the first time to prevent the migration and sublimation of disperse dyes in polyester fibers, and discovered a sheet-like structure and a method for producing the same that have an extremely excellent prevention effect using a plasma polymerization method. Ta. In addition to SPA, the present inventors conducted a detailed study on the effect of Galanu transition temperature Tg of thin films, but could not find any effect of SP value to prevent #de etc.

That is, the present invention provides the following features: [υ] 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 a resin layer, and a thin film with a thickness of 100 to 10,000× is coated on the surface of the at least one side of the resin layer. A sheet-like structure having an excellent effect of preventing disperse dye migration and sublimation, which is characterized by forming layers.

2. The sheet-like structure according to claim 1, wherein the thin film layer is made of a fluorine-containing compound or a silicon-containing compound.

3. A sheet-like structure according to claim 1 or 2, characterized in that the sheet-like structure satisfies the following formula.

y>-x+500 (x≧0y≧O) Bleeding A sheet-like structure in which at least one side of an R fiber structure containing 0% by weight or more of polyester fibers dyed with a disperse dye is treated with a resin and coated with a resin layer. What is the solubility parameter sp value of the disperse dye? > Perform low-temperature plasma polymerization using chemical agents having sp values different from O, S or more to form a thin film layer with a thickness of 100 to 100 X on the surface of the resin layer on at least one side of the sheet-like structure. A method for producing a sheet-like structure having an excellent effect of preventing disperse dye migration and sublimation, characterized by the following.

5. The method for producing a sheet-like structure according to claim 4, wherein the omega-containing monomer is a fluorine-containing monomer or a silicon-containing monomer.

e. The sheet-like structure according to claim 4 or 5, characterized in that the low-temperature plasma polymerization is carried out in a low-temperature plasma device having a non-grounded electrode insulated from the can body. manufacturing method.
”.

The fibrous structure referred to in the present invention refers to knitted and woven fabrics, nonwoven fabrics, etc., and naturally includes those that have been 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, annuraquinone, quinoline, quinone, phthalon, etc.
A combination of more than one type of dye may be used.

The polyester referred to in the present invention refers to aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalene-2,6-dicarboxylic acid, aliphatic dicarboxylic acids such as phthalic acid, adipic acid, and sepacic acid, or esters of these and ethylene. Glycol, diethylene glycol, ]-4-
Polyesters synthesized from diol compounds such as butanediol, neopentyl glycol, dichlorohexane-1,4-dimetatool, etc. are preferred, particularly polyesters in which 80% or more of the repeating structural units are ethylene terephthalate units. Furthermore, the above polyester component may be copolymerized with polyalkylene glycol, glycerin, pentaerythritol, methoxypolyalkylene glycol, bisphenol A1 sulfoisophthalic acid, etc., or may be mixed with a matting agent, heat stabilizer, pigment, etc. Naturally, these may be used. It is not limited to.

Furthermore, polyester fibers may of course be short fibers or long fibers, and also mean conjugates of polyester and other fibers, core-sheath fibers, multicore core-sheath fibers, and the like.

In short, the object is a fiber structure in which polyester fibers are dyed with a disperse dye and contain 10% by weight or more of the fibers. Containing 10% by weight or more may include various methods such as mixed fibers, mixed spinning, mixed knitting and weaving. When the amount is as small as 10% by weight, migration and sublimation of disperse dyes does not pose a major problem. The effect of this invention becomes remarkable at 10% by weight or more.

Resin processing refers to resin processing that is generally performed.
At least one side K of the fiber structure, although not particularly limited,
This is carried out using methods such as dip nip method, immersion method, coating method, and lamination method.

In terms of the effects of the present invention, latex such as polyurethane, polyacrylic acid ester, polymethacrylic acid ester, styrene-butadiene rubber, etc., which have severe migration sublimation, coated products and laminates such as polyvinyl acetate, chlorosulfonated polyethylene, polyvinyl chloride, etc. Particularly effective for objects. This is considered to be because the sp value of the solubility parameter of the disperse dye and the sp value of these resins are close to each other. In addition, these resin treatments are not limited to one type of resin, and may be performed using mixed resins or repeated resin treatments one or more times.The layer formed from these is called a resin layer, so the resin layer can be multilayered. It may happen. However, in this specification, these are considered more as resin layers.

The solubility parameter sp value is IV-33 of Polymer Handbook r7-337 to IV-359 pages.
Group Mo1ar At described on page 9 B2 or B1
5P=dXG/
This is a value calculated using the M formula, but SP of a representative substance
The value calculation results show that polyethylene terephthalate (1
0,7), polyurethane (8-10), polybutyl acrylate (8,5-9.5), polyvinyl chloride (9°5)
, disperse dye (8,3 to 9.7).

In this way, the disperse dye 5Pffi is the sp of polyester.
Since the SP value is close to that of polyurethane, polyacrylic acid ester, polyvinyl chloride, etc., the disperse dye migrates to the resin layer with good compatibility.

Dye Solubility Buff Meter SP , the value obtained by multiplying and adding the sp value of each dye by the blending ratio is taken as the average sp value, and the monomer has an sp value that differs from the average sp value by 0.5 or more. Of course, if more than one type of dye is blended, the dye has an SP value that is at least 0.5 smaller than the smallest SP value among the dyes, or the dye has a dye that has an SP value that is 0.5 or more smaller than the smallest SP value. If a chemical agent having an sp value of 5 or more is used, the effect of preventing migration and sublimation will be even more remarkable. Also, when using a mixture of dyes, the average sp value should be used in the same manner as in the case of blending disperse dyes. Examples of these chemical agents include aliphatic fluoride (
5,5-6.2), aromatic fluorocarbon (7,5-8.2
), various silane coupling agents (4,7-8.4), saturated hydrocarbons (8 or less), unsaturated hydrocarbons (8 or less), ethers (8 or less), ammonia (16,3), aliphatic lower There are gaseous substances and liquid substances such as alcohol (11-14,5), and any of them may be used.

According to the study results of the present inventors, the reason is not clear, but
Fluorine-based or silicon-based monomers are particularly effective. Examples of the fluorine yarn thread include gases such as CFa, C2FA, Freon, and C5Fs, and solutions such as acrylate of alkyl fluoride. Examples of silicon-based monomers include various silane coupling agents.

Using these polymers, a plasma polymerized thin film layer having a thickness of 100 to 10,000× is formed on at least one side of the resin layer. The sheet-like structure consisting of at least three layers obtained by these series of operations is a completely new structure. 10 obtained only by plasma polymerization method
A thin film of 0 to 1 oooo The fact that dye transfer and sublimation can be prevented with such a thin film shows how uniform the thickness of the plasma polymerized film is and that it is free from mottling. In addition, adhesion to the resin layer was very poor with conventional methods, but with plasma polymerization, the adhesion was extremely good.

If the film thickness exceeds 100,001 mm, the texture tends to be a little hard, and if the thickness is too small, the film may be damaged due to friction or scratching, and the effect of preventing migration and sublimation in that area will be reduced. Easily fooled. That is, the film thickness is preferably 100 to 100X, and more preferably 500 to 3000
It is X.

Further, if this sheet-like material satisfies the above-mentioned 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. Film thickness is 10
If it exceeds 000 i, the water resistance will increase, but the moisture permeability will decrease and the above formula will not be satisfied. Also, the film thickness is 100
If the thickness is small, the effect of improving water resistance will be somewhat small.

A sheet-like structure coated with a resin layer containing polyester fibers dyed with disperse dye has an ultra-thin film on the outermost layer, and there is no dye migration or sublimation, and this structure has moisture permeable and waterproof functions. It's the first time.

Furthermore, the low-temperature plasma polymerization method (processing) referred to in the present invention refers to a polymerization method that utilizes low-temperature one-fusma discharge, in which one or more monomers are supplied during discharge, and the process is carried out in the presence or absence of a non-polymerizable gas. (Method A), or the resin-treated fiber structure is subjected to low-temperature plasma discharge in the presence of a non-polymerizable gas to generate radicals.
When polymerizing by introducing into an atmosphere containing more than one type of polymerizable monomer (method B), or exposing the resin-treated fiber structure to an oxygen-containing atmosphere by subjecting it to low-temperature plasma discharge in the presence of oxygen gas or non-polymerizable gas. Peroxide method (method C) in which radicals are changed into peroxides, introduced into an atmosphere containing one or more types of polymerizable hexamer, and polymerized.
Including etc.

Low-temperature plasma refers to plasma generated during discharge with an average electron energy of 10 eV (10' to 10' K
), it is characterized by an electron density of 109 to 1012 ci'', and is also called non-equilibrium plasma because no equilibrium is established between the electron temperature and the gas temperature. , atoms, molecules, etc. are mixed.

Any frequency power source can be used to apply the voltage. In terms of continuity and uniformity of discharge, I KHz
= 10 GHz is desirable. In terms of plasma uniformity in the width direction of the electrode, IIGfz to I MHz is preferable, and if it exceeds I MHz and the length of the electrode exceeds 1 m, processing spots are likely to occur in the length direction. Further, at a frequency of 100 Hz or less, the edge effect of the electrode tends to occur, and arc discharge tends to occur at the edge portion. Further, as the current, alternating current, direct current, alternating current with Paianu applied, pulse wave, 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 plasma loses its activity and the plasma is scattered and the 1 fusma concentration is diluted, resulting in little processing effect.

Since the unidirectional electrode method allows the discharging electrode to be installed near the object to be treated, the treatment effect is greater than that of the external electrode method.

Electrode shapes can be divided into symmetrical and asymmetrical. In the case of a large-sized single-laser processing apparatus in which the object to be processed is large during processing and therefore requires a large electric field, symmetrical electrodes have more disadvantages. For example, uniform flow of gas between large electrodes is #1
It is almost impossible to do this, and furthermore, the electric field is disturbed at the ends of large electrodes, and 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 at 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.

One or more electrodes on the side that does not come into contact with the object to be treated can be arbitrarily selected, such as a cylindrical shape or a rod-like shape with a polygonal cross section having an acute angle, but the processing effect also differs depending on the number of electrodes. However, 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.

Further, as the material of the tWS, metals such as stainless steel, copper, iron, and aluminum can be used, and if necessary, it may be coated with glass, ceramics, etc. Naturally, these electrodes may be water-cooled if necessary, 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 little cine purity as possible;
This is not particularly the case if 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 order to avoid a gas short bath in 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 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, etc. The monomer gas, the 7-mer gas, and other gases can be introduced separately into the vacuum system and mixed within the system, or there is nothing wrong with mixing them in advance and introducing them at the same time. Below, you may introduce nanatsuma gas.

The degree of vacuum that generates low-temperature plasma is 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 decreases to 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 processing efficiency slightly decreases. . 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 degree is 5T
When the value exceeds orr, 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 sheet-like structure disposed between the electrodes has been described above, processing efficiency is generally good if the sheet-like structure is disposed in contact with one of the electrodes. In addition, if you do not want to apply tension to the structure or wrinkle the structure, use a type that allows the structure and electrode to move together, such as placing the structure in contact with the drum tfM. However, it is desirable that the structure be moved while rotating the drum. In fact, minute wrinkles often cause processing spots. If there is no need to pay special attention to tension or wrinkles, the structure may be placed in contact with the plate electrode, for example, and the structure may be moved by sliding on the electrode. Of course, after single-sided treatment, double-sided treatment becomes possible by passing through a place where the electrode is arranged opposite 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 treatment effect on both sides using only one pair of [4iMs], a sheet-like 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. Considering this phenomenon in terms of discharge characteristics, it can be explained by the voltage drop characteristics between the two electrodes. The voltage drop characteristics between both electrodes are
It is said that the voltage drop near the low-voltage side electrode is the largest, followed by the high-voltage side, and the voltage drop near the middle of the two electrodes is small. This is probably because the part where the fall is large can give more energy to the charged particles. In the case of a DC system, the low voltage side electrode and the high voltage side electrode are easily determined, but in the case of an AC system, the low voltage side and high voltage side alternate over time, so the low voltage side electrode and the high voltage side electrode cannot be distinguished. However, in any case, it is thought that the closer the electrode is, the greater the voltage drop and the greater the treatment effect.

Next, from the point of view of uniformity of treatment, both gL poles 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 5c11 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 the length of the kernels 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 the sheet-like structure means that
This device can continuously move sheet-like structures in the atmosphere into a vacuum system and process them, and the sheet-like structures can be placed in a pre-vacuum system and moved to a processing chamber. This refers to a structure in which structures are arranged in partitions, but in short, any structure in which the sheet-like structure can be moved continuously may be used. It is desirable that the Gufusma output is 0.1 to 5 watts/j as the output acting on the discharge portion.

In this case, the area of the discharge part is the area of the sheet-like structure existing in the discharge part or the surface area of the counter electrode divided by the value of the appearance of the discharge part, whichever value is 0.1. It should be ~5 watts/c11. The output of the discharge section can be easily calculated by measuring the voltage and current of the discharge section, but as a guide, it should be 30 to 70% of the output of the plasma power supply.
You may think so.

When the plasma output is less than 0.1 W/1, the plasma polymerization process takes time and the thickness of the polymerized film is not sufficient. When the plasma output exceeds 5 watts/cM, 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. If the treatment time is less than 5 seconds, the thickness of the polymerized film will be slightly low, and if the treatment time exceeds 600 seconds, the thickness of the polymerized film will be sufficient, but the fiber will become colored, the surface will become slightly hard or brittle, and the original performance of the fiber will be impaired. It may be different.

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, if a monomer with an average SP value that is 5 or more apart from the average SP value of the disperse dye is used and a thin film with a film thickness of 100 to 10,000X is used, migration and sublimation of the dye can be completely prevented. It has been found. Even if the film thickness is 100X or less, it is effective, but there is a slight drawback in friction durability. In addition, in order to obtain sufficient durability, preferably the film thickness is 500X or more.
good. However, depending on the type of monomer or resin, 100X
Some have sufficient durability.

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 (earth potential because it is grounded) are different. It does not act as a pole, and discharge occurs mainly between the two electrodes. Therefore, the plasma acts on the sheet-like structure without being effectively diluted, significantly increasing the treatment effect. At the same time, the treatment effect is significantly greater with less discharge power than the conventional grounding method, and the specified treatment can be achieved in a short time. Since the effects can be obtained, the device can be made smaller, or in other words, the equipment cost can be reduced.Moreover, since the discharge power is reduced, the running cost can be reduced to about a fraction.

A sheet-like structure in which a membrane obtained by plasma polymerization is formed on the resin-processed surface of a fibrous structure surprisingly does not impair the air permeability and moisture permeability of the resin-processed fibrous structure. In the case of a polymer film obtained using a fluorine-based or silicon thread coating, the water resistance and water repellency were improved.

A detailed explanation will be given below using examples. It is water repellent,
Water pressure resistance, air permeability, and moisture permeability are JIS L-1092 (spray method), JIS L-1092 (A method), JIS L
-1096A method (Fragile method), JIS K-632
Measured according to the 8-5-3-12 method, and washed by JI
Durability was evaluated by performing the test 10 times according to the SL-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 stainless steel plates.
The sample was placed in an atmosphere at 120°C under a load of 1000 m for 80 minutes, and the degree of contamination of the white background was determined using gray scale.

The measurement was performed twice in a dry state and in a wet state. In addition, the plasma device used in the example was a Pelger type and adopted a high frequency of 500 KHz as a power source.
The electrodes are symmetrical disc electrodes. Polymerization method A method in the example table,
Methods B and C correspond to the plasma polymerization methods A, B, and C in the patent specifications, where A is usually called plasma polymerization, B is a two-stage grafting method, and C is a peroxide method. It is.

C2F4 is an abbreviation for monomer, and C2F4 is tetrafluoroethylene.
TMC8 is trimethylchlorosilane, VDEMS is vinyldiethylmethylsilane, CHa is methane, VTAS is vinyltriacetoxysilane, and NH3 is ammonia.

The non-polymerizable gas Ar is argon, and 02 is oxygen.

In addition, durability was evaluated as ○ if the performance was 90% or more of the initial performance after 10 washes.

From Comparative Example 1, Example 1.2.4, and Comparative Example 2 in Table 1, it can be seen that plasma polymerization of 02F4 exhibits good dye transfer and sublimation properties at a film thickness of 100X or more.

It can also be seen that properties such as water pressure resistance and water repellency are improved.

It can be seen from Examples 2 and 3 that film formation is carried out efficiently by insulating the electrode plate of the plasma irradiation device from the can body.

Example 5.6.7 and Comparative Example] Yo, 9 TM01, V
DEMSf) Dye transfer sublimation property also by plasma polymerization,
It can be seen that the water pressure resistance and water repellency are improved.

In Example 8, active points were formed on the surface of a sheet-like structure by gas discharge, and then VDEMS was completely removed to cause a Sibraft reaction to occur at the active points. In Example 9, peroxide was formed on the surface of the sheet-like structure by gas discharge, and then VDEMS was introduced and the electrode plate was heated at 80°C.
The mixture was heated to cause a ff reaction (graph). Example 8.9
Both exhibited good dye migration and sublimation properties, water resistance, and water repellency.

Actual J[10 is an acrylic coated product subjected to methane gas plasma polymerization. It showed better dye transfer and sublimation properties than Comparative Example 3.

Examples 11, 12, and 13 are the results of plasma polymerization performed by changing the type of monomer and changing the difference between the average spa of the disperse dye and the average SP value of the monomer. Although VTAS has an SP value that is 0.6 lower than the average SP value of disperse dyes,
Since the difference from the minimum spa of the disperse dye is less than 0.1, the effect of improving dye transfer and sublimation is slightly lower than that of other VDEMS and NHs, but it is significantly improved compared to Comparative Example 4.

Example 14 contains 1/1 of C2F4 and CH4 in cotton blend PET.
This is the case where plasma polymerization is performed using a gas mixed with Comparative Example 5K < Dye migration, sublimation, water pressure resistance, and water repellency were significantly improved, but air permeability and moisture permeability remained unchanged. Moreover, the durability was also good.

Below is the blank space Procedure Amendment Bud (spontaneous) August 23, 1985 Patent Application No. 21350 of 1985 2 Title of invention Sheet-like bookkeeping article and its manufacturing method 3 Person making the amendment Relationship with the case Patent applicant 1621 Sakazu, Kurashiki City (1081 RiRa Co., Ltd. 2045-1 Aoeyama, Sakazu, Kurashiki City) RiRa Co., Ltd. - "Claims" column of the specification and "Detailed Description of the Invention"
Column I\6, Contents of amendment (1) The statements in the specification, special features, and fF claims are amended as in Attachment 3.4.

(2) Replace "8-95" on page 7, line 11 of the specification with r 8-9.5 (cal/cj)'J
K Correct.

(8) Page 7, line 6 of the specification (JIS K-6328)
-0208) Corrected to J.

(4) Ministry of Specification, page 7, line 13 (9th line from the bottom) “0.
5 or more J 'fr r O, 5 (cal/cj) '/
Correct to ``z or more''.

(5) Detail V 11th negative, 10th line ``Calculated value'' is changed to ``Calculated value ((cal/ad) 1'2] J KU Positive - t
Le.

(6) Specification page 19, line 10 r O,01~5oTorr J to r O,01~5.
0 Torr J K Correct.

(A) Specification page 25% Lines 10-11 r JI
SK-6328-5-3-12 method” rJIS Z-
0208 Act”.

+8) F94 thin V page 29, 91OJ middle, 4' from the left.

(9) Page 30 of the specification, 2 of Table 1 is corrected as shown in the attached sheet.

αQ Insert "〃" in the resin processing column of Comparative Example 4 in Table 1, page 31 of the specification.

αη Specification page 32, 4 of Table 1 is corrected as shown in Attachment 2.

Attachment 3 2. Claim J) Polyester fibers dyed with disperse dye]
A resin layer is coated on at least one side of the fiber structure containing 0 weight or more, and a resin layer is coated on at least one side with a film thickness of 10 weight.
A sheet-like structure having an excellent effect of preventing disperse dye migration and sublimation, characterized by forming a thin film layer of 0 to 100 OOA.

2) The sheet-like structure according to claim 1, wherein the thin film layer is made of a fluorine-containing compound or a silicon-containing compound.

3) A sheet-like structure according to claim 1 or 2, characterized in that the sheet-like structure satisfies the following formula.

y>-x+500 (x≧Oy≧0) 4) At least Attachment 4 A sheet of fiber structure containing 10 or more layers of polyester H dyed with disperse dye and coated with a resin layer by resin processing on one side. The bath solubility parameter sp value of the disperse dye is
, 5 (by performing low-temperature plasma polymerization using a monomer having an sp value of ca Millet h or more, and having a film thickness on the surface of the resin layer on at least one side of the sheet-like structure) 00 to 1
A method for producing a sheet-like structure having an excellent effect of preventing disperse dye migration and sublimation, the method comprising forming a thin film layer of 00OOA.

5) A method for manufacturing a sheet-like structure according to claim 4, characterized in that the monomer is a silicon-containing monomer. 6. A method for producing a sheet-like structure according to claim 4 or 5, characterized in that the method is carried out using a low-temperature plasma apparatus having an insulated non-grounded electrode.

Claims (1)

[Claims] 1) polyester fiber dyed with disperse dye
At least one side of the fiber structure containing 0% by weight or more is coated with a resin layer, and the surface of the at least one side resin layer is coated with a film thickness of 1%.
A sheet-like structure having an excellent effect of preventing disperse dye migration and sublimation, characterized by forming a thin film layer of 00 to 10,000 Å. 2) The sheet-like structure according to claim 1, wherein the thin film layer is made of a fluorine-containing compound or a silicon-containing compound. 3) A sheet-like structure according to claim 1 or 2, characterized in that 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 (J
IS K-6328) X: Water pressure resistance of sheet-like structure, mm (JIS L-1092) 4) Polyester fiber dyed with disperse dye
A monomer having an SP value different by 0.5 or more from the solubility parameter SP value of the disperse dye is used in a sheet-like structure in which at least one side of a fiber structure containing 0% by weight or more is resin-treated and coated with a resin layer. A sheet-like structure having an excellent effect of preventing disperse dye migration and sublimation, characterized in that a thin film layer of 100 to 10,000 Å in thickness is formed on the surface of the resin layer on at least one side of the sheet-like structure by performing low-temperature plasma polymerization processing. How things are manufactured. 5) The method for producing a sheet-like structure according to claim 4, wherein the monomer is a fluorine-containing monomer or a silicon-containing monomer. 6) The sheet-like structure according to claim 4 or 5, wherein the low-temperature plasma polymerization is performed in a low-temperature plasma apparatus having a non-grounded electrode insulated from the can body. How things are manufactured.