JPH09316766A - Colored fiber sheet and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a colored fiber sheet excellent in all of the coloring properties, color fastness to rubbing and touch feeling and provide a method for producing the colored fiber sheet. SOLUTION: This colored fiber sheet consists essentially of a fiber bundle containing an ultra superfine fiber having <=1.5μm fiber diameter or further superfine fiber having 1.5-4μm fiber diameter and a pigment is made to adhere thereto with a binder and further fixed thereto by heat treatment. The method for producing the colored fiber sheet comprises a step for producing the fiber sheet consisting essentially of the fiber bundle containing the ultra superfine fiber, a step for adding the pigment to the fiber and making the pigment adhere to the fiber and a step for fixing the pigment thereto by heat shrinking treatment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored colored fiber sheet excellent in fastness, texture and color development and a method for producing the same.

[0002]

2. Description of the Related Art A fiber sheet using ultrafine fibers having a denier of 0.5 denier or less is excellent in texture (flexibility), and thus is suitable for use in clothing, for example. In particular, it is necessary to color the fibers to meet consumer preferences.

Several dyeing techniques are known as methods for coloring the above ultrafine fibers. Generally, the smaller the fiber diameter is, the larger the fiber surface area is. When it is dyed with, the color developability tends to deteriorate. Therefore, it is necessary to dye with a larger amount of dye than usual in order to improve the color developability, but this causes a problem that the fastness is deteriorated.

When a colored artificial leather is formed by using the above fiber sheet, a method of coloring by mixing a pigment with the urethane resin when the artificial leather is manufactured by impregnating the urethane resin It has been known. However, the artificial leather colored by this method also has a problem that the friction fastness is poor.

Further, even if the raw dyed ultrafine fibers in which the pigment is kneaded are used, it is difficult to color the pigment deeply because the amount of the pigment that can be kneaded is limited.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a colored fiber sheet which solves the above problems and is excellent in color developability, fastness to rubbing and texture, and a method for producing the same.

[0007]

Means for Solving the Problems The present inventor has conducted diligent research to solve the above-mentioned conventional problems, and is a colored fiber sheet colored with a pigment, and further, the coloring property, the friction fastness, We have succeeded in developing a colored fiber sheet excellent in texture and texture and a method for producing the same.

More specifically, the present invention provides a fiber diameter of 1.5.
The present invention provides a colored fiber sheet which is mainly composed of a fiber bundle containing ultrafine fibers of not more than μm and which is colored with a pigment. Here, the "fiber bundle" means that at least one of ultrafine fibers and ultrafine fibers is present within a range of 10 times the diameter of the ultrafine fibers in the thickness direction of the ultrafine fibers. It means that any one of them maintains a substantially parallel state to each other over 50 μm or more in the length direction of the ultrafine fibers.

Further, in the present invention, when the cross-sectional shape of the ultrafine fibers or the ultrafine fibers is not circular, the diameter when the circles have the same cross-sectional area is taken as the fiber diameter.

Further, the present invention provides a colored fiber sheet which is mainly composed of a fiber bundle also containing ultrafine fibers having a fiber diameter of 1.5 μm to 4 μm and which is colored with a pigment.

The present invention also provides the above-mentioned colored fiber sheet, wherein at least one of the ultrafine fibers and the ultrafine fibers is polypropylene.

The present invention also provides the above-mentioned colored fiber sheet, wherein the ultrafine fibers are polypropylene and the ultrafine fibers are polyamide.

Further, the present invention provides the colored fiber sheet, wherein at least one of the ultrafine fiber and the ultrafine fiber is a primary fiber. is there. Here, the primary fiber means a fiber obtained by kneading a pigment into the fiber.

Further, according to the present invention, a pigment is fixed with a binder to a fiber sheet mainly composed of a fiber bundle containing ultrafine fibers having a fiber diameter of 1.5 μm or less, and the fiber sheet obtained by fixing the pigment with the binder is It relates to a method for producing a colored fiber sheet mainly composed of a fiber bundle containing ultrafine fibers having a fiber diameter of 1.5 μm or less, which is characterized by heating at a shrinkage temperature of the ultrafine fibers or higher and a melting point or lower to be colored. is there. Here, "fixing a pigment to a fiber sheet with a binder" means that the binder component uses the pigment particles as an adhesive to form at least one of fibers and a fiber bundle.
It means that it is adhesively held on at least one of the surface and the inside.

Further, in the present invention, a fiber sheet mainly composed of a fiber bundle containing ultrafine fibers having a fiber diameter of 1.5 μm or less is subjected to a hydrophilic surface treatment, and a pigment is fixed to the treated fiber sheet with a binder. A fiber bundle containing ultrafine fibers having a fiber diameter of 1.5 μm or less, characterized in that the fiber sheet having the pigment fixed with a binder is heated and colored at a temperature not lower than the contraction temperature of the ultrafine fibers and not higher than the melting point. The present invention relates to a method for producing a colored fiber sheet, which is mainly used.

Further, the present invention is the above-mentioned method for producing a colored fiber sheet, wherein the fiber bundle constituting the fiber sheet further contains ultrafine fibers having a fiber diameter of 1.5 μm to 4 μm. The present invention relates to a method for manufacturing a fiber sheet.

Further, the present invention relates to the method for producing a colored fiber sheet, wherein at least one of the ultrafine fibers and the ultrafine fibers is polypropylene. It is a thing.

Furthermore, the present invention is a method for producing a colored fiber sheet as described above, characterized in that the ultrafine fibers are polypropylene and the ultrafine fibers are polyamide. It is about.

The present invention also relates to a method for producing a colored fiber sheet, which is the above-mentioned colored fiber sheet, wherein at least one of the ultrafine fibers and the ultrafine fibers is a primary fiber. Is.

The present invention will be described in more detail with reference to the embodiments of the invention.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION

(Fiber Sheet) The colored fiber sheet according to the present invention is mainly composed of a fiber bundle containing ultrafine fibers having a fiber diameter of 1.5 μm or less (more preferably 1 μm or less, most preferably 0.5 μm or less). . Preferably, the ultrafine fibers are contained in the fiber bundle in an amount of 5% by weight or more (more preferably 10% by weight or more). In this case, the effect of fixing and holding the pigment by the heat shrinking step described below can be sufficiently achieved. The colored fiber sheet according to the present invention is obtained by further fixing a pigment to the above fiber sheet with a binder and coloring. Further, ultrafine fibers having a fiber diameter of 1.5 to 4 μm (preferably 1.5 to 3 μm) can be mixed in the fiber bundle according to the present invention. Specifically, the ultrafine fibers can be mixed in the fiber bundle in the range of 20 to 95% by weight, and the preferable range is 30 to 90% by weight. In the heat shrinking step described below, the presence of the ultrafine fibers suppresses shrinkage of the entire fiber sheet, exhibits excellent morphological stability, and further enhances the strength of the fiber sheet. The ultrafine fibers and / or the resin component constituting the ultrafine fibers constituting the colored fiber sheet according to the present invention include polypropylene, nylon, polyester,
Vinyl polymers such as polyurethane, polyacrylonitrile, and polystyrene can be preferably used. Particularly, the ultrafine fibers are preferably polypropylene, and the ultrafine fibers are preferably polypropylene or polyamide (for example, nylon 6).

Further, in order to obtain more excellent color developability, it is preferable that the ultra-fine fibers and / or the ultra-fine fibers are primary fibers. When the ultrafine fibers and / or the ultrafine fibers are made of polypropylene, the heat shrinking step described below can be carried out at a relatively low temperature, and further, it has excellent characteristics that it has sufficient heat resistance in practical use. .

Furthermore, when at least one of the ultrafine fibers and the ultrafine fibers is made of nylon, the obtained colored fiber sheet exhibits excellent texture and further excellent heat resistance. Also, because it has excellent wettability,
When a pigment dispersed in an aqueous solvent is used, it exhibits more uniform and excellent colorability.

Further, in the case of a fiber bundle composed of a combination of nylon ultrafine fibers and polypropylene ultrafine fibers, polypropylene makes it possible to suppress unnecessary aggregation of nylon, and the resulting colored fiber sheet has a bulky and tactile feel. It will be excellent.

(Pigment) As the pigment usable in the present invention, various organic and inorganic pigments can be used without any particular limitation. As the organic pigment, phthalocyanine-based, anthraquinone-based, thioindigo-based, and azo-based pigments can be used, and as the inorganic pigment, chrome red, molybdenum red, Prussian blue, titanium white, carbon black, iron oxide, and the like can be used.

The amount of the pigment to be used can be selected depending on the kind of the fiber used, the fiber diameter, the purpose of use, the color developability of the pigment, etc., but is preferably 60% by weight based on the weight of the binder solid content described below. % To 1% by weight, more preferably 40% to 1% by weight. Furthermore, the particle size of the pigment that can be used (as a peak value in the particle size distribution) is preferably such that it can be retained in the gaps between the fiber bundles, and more specifically, in the range of 0.01 to 1 μm. It is preferably in the range of 0.05 to 0.5 μm.

(Binder or Adhesive) As the binder (adhesive) for fixing the pigment to the fiber used in the present invention, the kind, the mode of use, the concentration, etc., of the fiber to be used, the fiber diameter, etc. Can be selected at any time. As the adhesive component of the binder, for example, polyacrylic acid ester type, polyurethane type, polyester type, polyamide type, ethylene-vinyl acetate copolymer type, polyvinyl acetate type, polyvinyl chloride type, synthetic rubber type can be preferably used. is there. In the present invention, in order to obtain a soft texture and a high friction fastness, it is particularly preferable to use a polyacrylic ester adhesive having a glass transition temperature of 0 ° C. or lower.

In the present invention, the amount of the binder can be appropriately selected depending on the type of the fiber used, the fiber diameter, etc., but is 10% by weight to 0.1% by weight based on the weight of the fiber sheet (only the fiber excluding the binder etc.). %, More preferably 5% to 1% by weight. Within this range,
At the same time, it has excellent fastness without impairing the texture.

The mode of use of the binder is not particularly limited, and the binder may be dissolved in a suitable organic solvent before use, or may be prepared as an aqueous emulsion. In the present invention, since it is preferable to use an aqueous dispersion pigment that is easy to handle in the process, the binder is preferably prepared as an aqueous emulsion.

(Hydrophilic treatment) The hydrophilic treatment of the fiber sheet according to the present invention is generally for the purpose of imparting preferable hydrophilicity to the fiber surface of the fiber sheet, and the method is not particularly limited. That is, the coloring of the pigment fibers is made uniform,
The purpose is to enable coloration without color unevenness. In order to obtain good coloring uniformity, it is necessary to fix the pigment to the fiber in a state where the pigment is sufficiently dispersed in the binder. At this time, when the binder is prepared as an aqueous emulsion, the fiber sheet is used. Depending on the nature of the surface (including the surface of the internal fiber component), it is necessary to disperse the pigment using water or a suitable organic solvent.

That is, when the surface of the fiber sheet has a hydrophobic property, it is preferable to disperse the pigment in an emulsion of an aqueous binder using a suitable organic solvent and mix it with the binder emulsion. When the fiber surface is sufficiently hydrophilic or has been hydrophilically treated, it is not always necessary to mix the above organic solvents, and it is possible to obtain sufficient homogeneity simply by dispersing the pigment in an aqueous emulsion. Is.

(Fastness to rubbing) The colored fiber sheet according to the present invention having the above-mentioned constitution shows excellent fastness to rubbing, and JI
It shows a fastness of 3 or higher in both the dry test and the wet test using the friction tester type II based on the "dye fastness test method for friction" defined in S L0849. Moreover, it not only exhibits sufficient color development but also has an excellent texture.

(Post-Processing) The post-processing of the colored fiber sheet according to the present invention is not particularly limited, but it is a usual rubbing process, water repellent process, resin process, raising process such as puffing, greasing, and antistatic treatment. Agents, antibacterial agents, softening agents, etc. can be processed.

(Method for producing a colored fiber sheet) The method for producing a colored fiber sheet according to the present invention comprises (1) a step for producing a fiber sheet (preferably a non-woven fabric),
(2) fixing the pigment to the fiber with a binder,
And (3) a step of fixing the pigment by heat shrinkage treatment. Furthermore, before the step (2) above,
It is also possible to add a step of hydrophilic treatment of the fiber sheet.

The following will be described in order.

(1) Production of Fiber Sheet In the production of the colored colored fiber sheet according to the present invention, the method for obtaining the fiber sheet is not particularly limited, and a generally known technique (for example, published by the Business Development Center Publishing Department, Although the latest non-woven fabric manufacturing technology and practical application of various applications can be used), in the present invention, it is particularly preferable to use splittable fibers to obtain ultrafine fibers. Can be easily spun by a conventional composite spinning method, mixed spinning method, or a spinning method in which these are combined (for example, "Ultra Fine Fiber," issued by Osaka Chemical Marketing Center Co., Ltd.). New stage ”(issued March 10, 1984).

The splittable fiber has various shapes,
For example, there is one having a cross-sectional shape as shown in FIGS. The one shown in FIGS. 1 and 5 is a sea-island type, and FIG.
3 shows a multi-bimetal type, FIG. 3 shows a chrysanthemum type (or orange type), and FIG. 4 shows a combination of these (here, a chrysanthemum type and a sea island type are combined). There is a composite one). Although the present invention is not limited, the present invention is particularly
The splittable fiber for obtaining the ultrafine fiber is preferably a sea-island type fiber that easily forms a fiber bundle or a fiber having a sea-island type cross-section.

Particularly preferred in the present invention is a sea-island type fiber (FIGS. 1 and 4, which can be split by an external force such as fluid flow).
5). That is, since a finer fiber bundle can be formed, a better texture is given. The sea-island fiber shown in FIG. 1 or 5 is irregularly divided, and the sea-island fiber shown in FIG. 4 is likely to be regularly divided. In addition, the sea-island type fiber shown in FIG. 1 or 5 contains an island component having a diameter of 0.06 to 0.2 R relative to the fiber diameter R of the sea-island type fiber so that the splitting process is easy. preferable. The splittable fibers shown in FIGS. 1 to 5 easily give ultrafine fibers by an external force (for example, a fluid flow such as water flow, needle punching) or solvent extraction. In the case of obtaining ultrafine fibers by solvent extraction, it is preferable to entangle them with a fluid flow or a needle punch before solvent extraction so as to have excellent extraction workability and excellent nonwoven fabric strength. In particular, FIGS. 1, 4 and 5
When a splittable fiber as shown in (1) is used and a fluid flow or a needle punch is applied, the splittable fibers are split and entangled, so that the extraction workability and the strength of the nonwoven fabric are more excellent.

As a method of forming a fibrous sheet, particularly a fibrous web for producing a non-woven fabric, a dry method and a wet method have been conventionally used and can be suitably used in the present invention. In the present invention, the card method, the air-laying method, the melt-blowing method as a dry method that is more easily entangled,
Alternatively, the spun bond method is preferably used, and the card method or the air lay method is particularly preferable.

Conventionally, a method for binding a fibrous web to form a non-woven fabric is a method using a binder, a method utilizing the fusion property of fibers, a stitching method, and a method of entanglement by a fluid flow such as needle punch or water flow. It has been known. In the present invention, the method of entanglement by fluid flow is
It is one of the preferred methods because it is uniformly and densely entangled and does not prevent the pigment from penetrating into the fiber bundle. Further, by using sea-island type fibers (for example, FIGS. 1, 4, 5) that can be easily divided by an external force and applying a fluid flow, a finer fiber bundle can be obtained.

Next, at least one resin component of the splittable fibers is extracted and removed to form a fiber bundle containing ultrafine fibers. In particular, when the sea-island type fiber or the fiber having the sea-island type cross-section is used, a fiber bundle containing many ultrafine fibers can be formed, and this fiber bundle is excellent in pigment retention.
This extraction and removal can be performed, for example, by immersing at least one resin component of the splittable fiber in an extractable solvent.

In the present invention, when at least one resin component of the splittable fiber is extracted and removed to form a fiber bundle and then a fluid flow is further applied, the surface resistance of the non-woven fabric is improved. is there. Particularly, when the fiber diameter of the ultrafine fibers is 0.5 μm or less, not only the surface resistance is improved, but also the fiber bundle is slightly opened by this fluid flow, and the pigment easily enters the fiber bundle. It is preferable because it improves the fastness.

(2) Fixation of Pigment with Binder In the present invention, there is no particular limitation on the method of fixing the pigment to the fiber with the binder. Generally, a fiber sheet is dipped in a solution prepared by mixing a binder and a pigment in a predetermined concentration in a suitable solvent, and then the excess solution is removed, followed by a drying treatment to obtain a predetermined solid amount. It is possible to apply the binder and pigment of 1) and then dry and fix the pigment to the fiber with the binder.

At this time, when the binder is prepared as an aqueous emulsion, the pigment is water or
It is easily possible to disperse using a suitable organic solvent and mix with the binder emulsion.

Alternatively, a splittable fiber capable of generating a super-fine fiber and / or a super-fine fiber as a raw fiber, or a splittable fiber which does not generate a split fiber and a raw fiber and / or another raw fiber It is also possible to produce a fiber sheet by mixing and further color the obtained fiber sheet by the same method as described above.

(3) Fixing of Pigment by Heat Shrinkage Further, the method for producing a fiber sheet according to the present invention includes (2)
It is characterized in that the fiber sheet in which the pigment obtained in (1) is fixed to the fiber with a binder is heat-treated to fix the pigment particles to at least one of the vicinity of the fiber bundle and the inside of the fiber bundle. That is, the colored fiber sheet according to the present invention contains ultrafine fibers in the fiber bundle, preferably 5% by weight or more (more preferably 10% by weight or more), and the fibers are appropriately treated by the heat treatment. The pigment particles are contracted by a certain amount, and the pigment particles are retained in the fiber bundle, and as a result, the friction fastness is remarkably improved.

[0047] Here, the shrinkage temperature means a temperature at which contraction 1% or more, shrinkage, JIS L1015 ^- shall mean a value measured by the method specified in ¹⁹⁹² 7.15 shrinkage.

Therefore, it is preferable that the heat treatment according to the present invention is performed at a temperature higher than the shrinkage temperature of the ultrafine fibers and lower than the melting point of the fibers. The shrinkage temperature is set according to JIS
It is determined by the method specified in the standard, and the melting point can be determined based on DSC (differential scanning calorimeter) measurement. More preferably, the temperature is about 10 ° C. higher than the shrinkage temperature and about 10 ° C. lower than the melting point.

Further, the heat treatment is not limited to the case where the ultrafine fibers are made of one type (for example, polypropylene),
Similarly, when the ultrafine fibers are composed of a plurality of resin components such as polypropylene and nylon, the obtained colored fiber sheet is remarkably improved in friction fastness. In this case, the shrinkage temperature of polypropylene having a lower shrinkage temperature is used as a reference.

(4) Hydrophilic treatment method There is no particular limitation on the hydrophilic treatment method for the surface of the above-mentioned fibers which can be preferably used in the present invention, and various ordinary chemical treatments or physical treatments can be used. .
As the physical treatment preferably usable in the present invention, specifically, discharge treatment (plasma treatment)
Is mentioned. Particularly, in the present invention, a method of introducing hydrophilicity to a fiber sheet by electric discharge treatment using a Teflon sheet as a dielectric is preferable.

FIG. 6 shows an example of the outline of an apparatus for hydrophilic treatment which can be preferably used in the present invention. That is, the pair of electrodes 21 provided with the dielectric layers 41, 42 on the respective facing surfaces of the fiber sheet 11 and facing each other,
The fiber sheet 11 is disposed between the two electrodes 22 so that the pair of electrodes 21 and 22 do not come into direct contact with each other but the outer surfaces of the dielectric layers 41 and 42 come into direct contact with each other. Applying an AC voltage between them to generate a discharge in the internal void of the fiber sheet sandwiched between both electrodes,
It is a method of treating the entire surface of the fiber sheet. Here, the total surface includes the surface of the internal space formed by the constituent fibers in the fiber sheet, that is, the entire surface of each constituent fiber.

Furthermore, by pressing the electrodes 21 and 22 with an appropriate pressure, the electrodes 21 and the dielectric layer 41, the dielectric layer 41 and the fiber sheet 11, the fiber sheet 11 and the dielectric layer 42, and the dielectric Surface contact may be made between the body layer 42 and each of the electrodes 22 so as to form substantially no space. It is preferable that the electrodes 21 and 22 have a size smaller than that of the dielectric layers 41 and 42 with which the electrodes 21 and 22 are in contact, because the electrodes 21 and 22 do not come into contact with the fiber sheet 11. In addition, the size of the electrodes 21 and 22 is
When the sizes of the dielectric layers 41 and 42 that are in contact with each other are the same, the electrode 2 is provided by providing a covering material (for example, vinyl tape) made of a dielectric material around the electrodes.
It is possible to prevent the fiber sheets 11 and 22 from coming into contact with each other. The electrode 21 is connected to an AC power supply 51, and the electrode 22 is grounded.

Here, when an AC high voltage is applied from the AC power supply 51, it is left in the internal void of the fiber sheet 11 and plasma is generated. The plasma generated in the internal voids of the fiber sheet 11 acts on the internal surface of the fiber sheet 11, so that the internal surface of the fiber sheet 11 is modified. At this time, since the outer surface of the fiber sheet 11 is in contact with the dielectric layer 41 or 42, the fiber sheet 11
Ideally, the plasma generated in the internal void does not act on the contact point with the dielectric layer on the outer surface of the fiber sheet 11. In fact, the contact point is a very small area compared to the area of the outer surface, so that virtually all outer surfaces can be treated. Moreover, since the fiber sheet 11 is processed not only by the plasma but also by the radicals generated by the plasma, when the fiber sheet 11 and the derivative layer are separated, the contact points are also processed by the radicals remaining without being deactivated. It will be. Since the electric discharge is generated in the internal voids of the fiber sheet, the object to be treated is less likely to be damaged by the spark discharge or the like.

The lower limit of the AC voltage applied to generate a discharge by the AC power source depends on the distance between the electrodes including the dielectric layer and the type of gas, and is not particularly limited, but preferably 0.5 KVp -p or more, more preferably 1 KVp-p or more (KVp-p indicates the voltage difference from the maximum value peak to the minimum value peak of the AC voltage). This is because when the voltage is less than 0.5 KVp-p, discharge does not substantially occur.
The upper limit of the AC voltage is not particularly limited as long as it is a voltage that does not damage the fiber sheet. The frequency is not particularly limited, but is preferably 0.1 to 100 KHz, more preferably 1 to 50 KHz.
Hz. If the frequency is less than 0.1 KHz, the treatment efficiency due to discharge is reduced, and if it exceeds 100 KHz, the fiber sheet may be heated and damaged by dielectric heating. Since these values largely depend on the shape of each electrode, the material of the fiber sheet, the discharge voltage waveform, and the treatment time, they may be used outside the above range.

As the electrode material usable in the present invention, a conductor having a specific resistance of preferably 10 ³ Ω · cm or less, more preferably 10 ⁰ Ω · cm or less, can be used.
For example, metal (eg, stainless steel, aluminum, tugsten, etc.), conductive metal oxide, carbon, or conductor (eg, metal powder or carbon powder, etc.)
It is possible to use a conductive rubber, which is a composite of rubber and rubber.

As the shape of the electrode, for example, a needle electrode, a sheet electrode, a plate electrode, or a columnar electrode can be used. In particular, when the fiber sheet and the electrode move relative to each other, the fiber sheet itself rotates as the central axis of the cylinder in synchronization with the parallel movement of the fiber sheet so that the surface of the fiber sheet is less likely to be damaged. A cylindrical electrode that can be used is preferable.

The lower limit of the pressure applied between both electrodes is a pressure that ensures surface contact between the electrode and the dielectric layer and between the dielectric layer and the fiber sheet and does not substantially form a space.

Examples of usable dielectrics include:
Glass, ceramics (for example, alumina), rubber (for example, silicon or chloroprene), or a thermoplastic resin (for example, polytetrafluoroethylene or polyester) can be given. The thickness of the dielectric layer is not particularly limited, but may be 0.05 to 5 mm.
It is preferably about the same. If it is thicker than 5 mm, a high voltage is required for discharging, and if it is less than 0.05 mm, the mechanical strength is lowered and dielectric breakdown easily occurs.

The shape of the fiber sheet which can be totally surface-treated by the above method is not particularly limited as long as it has a void inside the fiber sheet under the processing conditions.

Generally, it is carried out in an open system (in air),
Electric discharge may be generated while supplying a surface treatment gas other than air to the internal voids of the fiber sheet.

The surface-treating gas that can be used in the present invention is not particularly limited, and a known surface-treating gas can be selected according to the desired surface treatment. Particularly, for the purpose of imparting hydrophilicity or improving hydrophilicity, specifically, air and oxygen gas can be preferably used.

The present invention will be described in more detail below with reference to examples.

[0063]

【Example】

(Examples 1 to 4) and (Comparative Examples 1 to 2) In a conventional sea-island type fiber composite spinning apparatus, polypropylene (MI: 21) was supplied from the nozzle serving as the island component, and polypropylene was used from the nozzle serving as the sea component. 60 parts of polyethylene terephthalate copolymerized with 5-sulfoisophthalic acid and polyethylene glycol and polypropylene (MI: 10) 4
A mixture of 0 parts and pellets was extruded at a gear pump ratio of 1: 1 and composite-spun at 240 ° C. to obtain a fineness of 0.6.
A wound yarn of 6 mg / m was obtained.

Next, this wound yarn was drawn 3.2 times at 90 ° C., then crimped and cut to give a fineness of 0.23 mg.
/ M (diameter R15.4 μm), a fiber length of 51 mm, and a number of crimps of 0.83 fibers / mm were formed. The cross-sectional shape of this sea-island type fiber is as shown in FIG.
25 thick island components (microfibers) with a circular cross section of 2 μm (0.13R) and a circular cross section of 0.22 μ in the sea component
m (0.014R) fine island component (ultrafine fiber) is about 15
00 pieces were dispersed.

Since the description of the cross section of the sea-island type fiber described in the examples of the present invention is difficult to observe with an electron microscope, the cross sectional state is a yarn spun from a nozzle and wound up. Is estimated from the result of sampling and observing with an optical microscope. Further, it is generally known that the cross-sectional state of a spun yarn is maintained even after drawing.

Next, the unidirectional fiber web in which the sea-island type fibers were formed by a card machine was crossed with a cross layer in the traveling direction of the fiber web to form a crossed fiber web. Next, this crossed fiber web was placed on a net having an opening of 0.147 mm, and then the diameter was 0.13 m.
The sea-island type fibers were split and entangled at the same time by jetting a water flow having a pressure of 7.8, 11.8, and 11.8 MPa alternately from both sides of a nozzle plate having m and a pitch of 0.6 mm.

Then, the entangled fiber web was heated at 80 ° C. for 10 minutes.
It was dipped in a weight% sodium hydroxide aqueous solution for 30 minutes to decompose and remove the copolymerized polyethylene terephthalate, which is a sea component, to form a nonwoven fabric having an areal density of 80 g / m ² and a thickness of 0.7 mm.

On the other hand, in a 30% by weight aqueous ethanol solution,
Phthalocyanine-based water-dispersed blue pigment (RYUDYE-WB
lue GLK; Dainippon Ink Co., Ltd., particle size (peak) 0.1 to 0.2 μm) and water-dispersed polyacrylate adhesive (DICNALV-18; Dainippon Ink Co., Ltd., Tg:- 45 ° C.) was mixed at a solid content ratio of 2: 5 to prepare a dispersion liquid having a total solid content concentration of 5%.

Then, this non-woven fabric was impregnated with this dispersion liquid so that the solid content was 4.5 g / m ^2, and then 100
Dry at 10 ° C. for 10 minutes.

Subsequently, after heat-treating at the temperature and time shown in Table 1, it was lightly kneaded to obtain a blue non-woven fabric having the areal density and thickness shown in Table 1. Table 1 also shows the shrinkage ratio (average value of the shrinkage ratio in the vertical direction and the shrinkage ratio in the horizontal direction) at the time of this heat treatment. The thickness is a value under a load of 20 g / cm ² .

(Table 1) Temperature Time Area Density Thickness Shrinkage (° C) (min) (g / m ² ) (mm) (%) Comparative Example 1 120 6 85 0.7 0.1 0.1 Example 1 130 5 87 0.7 1.4 Example 2 140 4 91 0.7 0.7 3.5 Example 3 150 3 96 0.7 6.1 Example 4 160 2 105 0.7 10.5 Comparative Example 2 170 1 213 0 7 37 (Example 5) 40 parts of polypropylene (MI: 10) and 5
A mixture of 60 parts of polyethylene terephthalate copolymerized with sulfoisophthalic acid and polyethylene glycol in a pellet state was extruded and mixed and spun at 280 ° C. to obtain a wound yarn having a fiber density of 0.66 mg / m 2.

Next, after stretching this wound yarn at 90 ° C. by 3.4 times, it is crimped and cut to a fiber length of 0.22 m.
A sea-island fiber having a g / m (diameter of 17.5 μm), a fiber length of 51 mm, and a number of crimps of 1.1 / mm was formed.

The sea-island type fiber has a cross section of 0.42 μm (0.02 μm) with a circular cross section as shown in FIG.
About 700 island components (polypropylene) of 4R) were dispersed. Except that this sea-island type fiber was used, the areal density was 100 g / m ² and the thickness was 0.1 g in the same manner as in Example 3.
A 7 mm colored nonwoven fabric was formed. The contraction rate is 8.2.
%Met.

Example 6 In a conventional sea-island type fiber composite spinning apparatus, polypropylene (MI: 65) was supplied from the island component nozzles, while polylactic acid was supplied from the sea component nozzles using a gear pump ratio of 3. Extrusion at 2: 9.6, 245
Composite spinning was performed at 0 ° C. to obtain a wound yarn having a weave of 0.44 mg / m.

Then, this wound yarn was drawn 4.3 times at 90 ° C., crimped, cut and weighed 0.11 mg.
/ M (diameter 11.1 μm), fiber length 38 mm, number of crimps 1.0 / mm, sea-island type fiber was formed.

The sea-island type fiber has a cross section of 1.2 μm (0.11 μm) with a circular cross section as shown in the fiber cross section of FIG.
25 island components (polypropylene) of R) were arranged. Except for using this sea-island type fiber, the areal density is 98 g / m ² and the thickness is 0.7 mm in the same manner as in Example 3.
To form a colored nonwoven fabric. The shrinkage rate was 7.2%.

Comparative Example 3 In a conventional sea-island type fiber composite spinning apparatus, polypropylene (MI: 65) was supplied from the nozzle serving as the island component, and polylactic acid was supplied from the nozzle serving as the sea component, with a gear pump ratio of 7. Extrusion at 3: 7.8, 245
Composite spinning was carried out at 0 ° C. to obtain a wound yarn having a weave of 0.64 mg / m 2.

Next, this wound yarn was drawn at 90 ° C. for 4.8 times, then crimped and cut to give a fiber of 0.15 mg.
/ M (diameter 12.7 μm), fiber length 38 mm, and crimp number 1.0 / mm.

The sea-island type fiber has a cross section of 1.9 μm (0.15 μm in diameter) with a circular cross section as shown in FIG.
25 island components (polypropylene) of R) were arranged. Except that this sea-island type fiber was used, the areal density was 96 g / m ² and the thickness was 0.7 mm in the same manner as in Example 3.
To form a colored nonwoven fabric. The shrinkage rate was 6%.

(Example 7) In a conventional sea-island type fiber composite spinning apparatus, nylon 6 was fed from a nozzle as an island component.
On the other hand, 60 parts of polyethylene terephthalate copolymerized with 5-sulfoisophthalic acid and polyethylene glycol and polypropylene (MI: 1
0) A mixture of 40 parts and pellets was extruded at a gear pump ratio of 6.5: 7, composite-spun at 280 ° C.,
A wound yarn having a fiber density of 0.66 mg / m was obtained.

Next, this wound yarn was drawn at 90 ° C. for 2.8 times, then crimped and cut to obtain a fiber of 0.24 mg.
/ M (diameter 16.7 μm), fiber length 51 mm, and number of crimps 1.1 / mm.

The cross section of this sea-island type fiber was indefinite due to its high compatibility, as shown in the cross section of the fiber in FIG.
25 thick island components (ultrafine fibers, nylon 6) with a diameter of 2 μm (0.12R) and a circular cross-section of 0.4 in the sea component
About 420 pieces of 1 μm (0.025R) small island components (ultrafine fibers, polypropylene) were dispersed. Except for using this sea-island fiber, in the same manner as in Example 3,
A colored nonwoven fabric having an areal density of 87 g / m ² and a thickness of 0.7 mm was formed. The shrinkage rate was 1.4%. Further, as compared with that of Example 3, the dimensional stability before and after the heat treatment was excellent, and the wettability when impregnating the dispersion liquid was excellent.

Example 8 A masterbatch containing polypropylene and a blue pigment was mixed in a pellet state so that the pigment content was 4.3% by weight. Then, in a conventional sea-island type fiber composite spinning device, the above pigment-containing polypropylene is supplied from the nozzle serving as the island component, while 60 parts of polylactic acid and polypropylene (MI: 10) are supplied from the nozzle serving as the sea component.
A mixture of 40 parts with pellets was extruded at a gear pump ratio of 1: 1 and composite-spun at 240 ° C. to obtain a fineness of 0.
A winding yarn of 85 mg / m was obtained.

Next, this wound yarn was stretched 4.8 times at 90 ° C., then crimped and cut to give a fineness of 0.21 mg.
/ M (diameter 15 μm), fiber length 51 mm, crimp number 0.9
The sea / island type fiber was formed at the number of pieces / mm.

The sea-island type fiber has a circular cross section with a circular cross section and a diameter of 2.3 μm (0.15
R) Twenty-five primed polypropylene thick island components containing 4.3% by weight of blue pigment, and a diameter of circular section 0.1 in the sea component.
8μm (0.013R) Hososhima component (polypropylene)
About 2000 were dispersed. An areal density of 96 was obtained in the same manner as in Example 3 except that this sea-island type fiber was used.
A colored nonwoven fabric having a thickness of 0.7 mm and a g / m ² was formed. The shrinkage rate was 6.1%. Further, it had a deeper color tone as compared with that of Example 3.

Example 9 In a conventional sea-island type fiber composite spinning apparatus, polypropylene was copolymerized from a nozzle serving as an island component, and 5-sulfoisophthalic acid and polyethylene glycol were copolymerized from a nozzle serving as a sea component. 60 parts of polyethylene terephthalate and propylene (MI:
10) A mixture of 40 parts and 40 parts in a pellet state was extruded at a gear pump ratio of 8: 15.8 and composite-spun at 290 ° C. to obtain a wound yarn having a fineness of 0.83 mg / m.

Next, this wound yarn was drawn 3.3 times at 90 ° C., then crimped and cut to give a fineness of 0.36 mg.
/ M (diameter 20.4 μm), fiber length 51 mm, and crimp number 1.1 / mm.

The sea-island type fiber has a cross section of circular cross section and a diameter of 2.6 μm (0.13) as shown in the fiber cross section of FIG.
21) of Taishima component (ultrafine fiber, polypropylene) of R) and a diameter of 0.13 μm (0.00
About 9000 fine island components (ultrafine fibers, polypropylene) of 64R) were dispersed. An areal density of 100 was obtained in exactly the same manner as in Example 3 except that this sea-island fiber was used.
A colored nonwoven fabric having a thickness of 0.7 mm and a g / m ² was formed. The shrinkage rate was 8%.

(Example 10) A non-woven fabric formed in exactly the same manner as in Example 9 was placed on a net having an opening of 0.147 mm, and a pressure of 6 from a nozzle plate having a diameter of 0.13 mm and a pitch of 0.6 mm. The fiber bundle was loosened by jetting out a water stream of .9 MPa. Then, in exactly the same manner as in Example 9, fixing with a binder and heat treatment were carried out to form a colored nonwoven fabric having an areal density of 101 g / m ² and a thickness of 0.7 mm. The shrinkage rate was 8.5%.

(Example 11) Using the sea-island type fiber used in Example 3, a web was formed in the same manner as in Example 3.
Water entanglement, sea component decomposition and removal, areal density 80g /
A nonwoven fabric having a thickness of m ² and a thickness of 0.7 mm was formed.

Then, the obtained non-woven fabric (fiber sheet)
According to the apparatus shown in FIG. 6, a flat plate stainless steel (width 160 mm, length 210 mm) is used for the electrode, a Teflon sheet (thickness 0.1 mm) is used for the dielectric, and 800 W AC is applied by the impulse electrode (frequency 5 kHz). Hydrophilicity was imparted by applying for 10 seconds in the air.

On the other hand, RYUDYE-W Blue GL
K and DICNAL V-18 were made into an aqueous dispersion having a solid content weight ratio of 2: 5 and a total solid content weight concentration of 5%, and the dispersion was impregnated into the nonwoven fabric so that the solid content became 4.5 g / m ^2. After the treatment, it was dried at 100 ° C. for 10 minutes.

Then, after heat treatment at 150 ° C. for 3 minutes,
Lightly knead and loosen, areal density 96g / m ² , thickness 0.7m
m blue woven fabric was obtained. The shrinkage ratio due to the heat treatment was 6.0%.

(Comparative Example 4) RYUDYE-W Blue GLK and D were used without the surface treatment used in Example 11.
ICNAL V-18 was made into an aqueous dispersion having a solid content weight ratio of 2: 5 and a total solid content weight concentration of 5%, and this non-woven fabric was impregnated so that the solid content became 4.5 g / m ^2. went. In this case, it took a long time for the dispersion liquid to permeate, and the inside of the fiber sheet could not be evenly adhered. Further, color unevenness was observed after drying. Further, a continuous coloring operation was tried, but it could not be practically performed due to the above problems.

(Fastness Test, Feeling Test, and Results) Wet Rubbing Fastness Test: Based on the JIS fastness test method for dyeing fastness (L0849), a friction tester type II was used.

Feeling test: The non-colored non-woven fabric and the non-colored non-woven fabric were compared, and when they were equivalent, they were evaluated as ◯, when slightly hard, as Δ, and when they became apparently hard as ×.

Color development test: The coloring of the colored nonwoven fabric of the present invention is based on the one obtained by coloring the nonwoven fabric formed in the same manner as in Example 7 (before coloring) under the following conditions (conditions for dyeing deep blue): The sex was evaluated.

Dye; Nylosan Blue N-G
FL (acid dye, manufactured by SANZOZ) 10% (% by weight of fiber) Bath ratio; 1:75 Dyeing condition; 130 ° C. × 60 minutes After dyeing, it was washed with water and dried.

◎ Excellent ○ Equal × Inferior

[0100]

The coloring method of the fiber sheet containing the ultrafine fibers according to the present invention is coloring with a pigment. Therefore, by selecting an appropriate pigment, it is possible to obtain a required color (color depth, depth, etc.) without being limited to the resin component constituting the ultrafine fiber. Further, the amount of the binder added is smaller than that in the case where there is no fiber bundle containing the ultrafine fibers, and therefore the texture of the fiber sheet containing the colored ultrafine fibers is not impaired. Further, in the present invention, since the pigment particles are more firmly fixed by the heat shrinkage of the ultrafine fibers, the binder for fixing the pigment particles to the fibers requires only a very small amount, and the obtained colored fiber sheet has a texture. (Softness) is not impaired.

Furthermore, in the present invention, the pigment fixed to the fiber is more firmly fixed due to the heat shrinkage of the ultrafine fibers, so that the obtained colored fiber sheet has extremely high friction fastness. . That is, it is estimated that the heat treatment causes the ultrafine fibers to contract, whereby the pigment particles are held in the fiber bundle. Therefore, an extremely excellent colored fiber sheet having a friction fastness of grade 3 or higher is provided.

Further, by hydrophilically treating the fiber sheet, it is possible to obtain a uniform colored fiber sheet without using an organic solvent.

[Brief description of drawings]

FIG. 1 is a diagram showing a schematic cross section of a sea-island type splittable fiber.

FIG. 2 is a diagram showing a schematic cross section of a bimetal-type splittable fiber.

FIG. 3 is a diagram showing a schematic cross section of a chrysanthemum-type splittable fiber.

FIG. 4 is a diagram showing a schematic cross section of a splittable fiber having a sea-island cross section.

FIG. 5 is a diagram showing a schematic cross section of a sea-island type splittable fiber.

FIG. 6 is a diagram schematically showing a hydrophilic treatment device of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Sea component, 2 ... Island component used as an ultrafine fiber or a superfine fiber, 3 ... Island component used as a superfine fiber, 11 ... Fiber sheet,
21, 22 ... Electrodes, 41, 42 ... Dielectric layer, 51 ... AC power supply

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D06M 7/02 A 10/00 L

Claims (11)

[Claims] 1. A colored fiber sheet mainly composed of a fiber bundle containing ultrafine fibers having a fiber diameter of 1.5 μm or less and colored with a pigment. 2. The colored fiber sheet according to claim 1, wherein the fiber bundle further has a fiber diameter of 1.5 μm to 4 μm.
A colored fiber sheet comprising m ultrafine fibers. 3. The colored fiber sheet according to claim 1, wherein any one of the ultrafine fibers and the ultrafine fibers is polypropylene. 4. The colored fiber sheet according to claim 2, wherein the ultrafine fibers are polypropylene and the ultrafine fibers are polyamide. 5. The colored fiber sheet according to claim 1, wherein at least one of the ultrafine fibers and the ultrafine fibers is a primary fiber. Fiber sheet. 6. A step of fixing a pigment to a fiber sheet mainly composed of a fiber bundle containing ultrafine fibers having a fiber diameter of 1.5 μm or less with a binder, and a fiber sheet obtained by fixing the pigment with a binder to the ultrafine fiber. A method for producing a colored fiber sheet, which comprises a step of heating at a temperature not lower than the shrinkage temperature of the fiber and not higher than the melting point. 7. A step of hydrophilically treating a fiber sheet mainly composed of a fiber bundle containing ultrafine fibers having a fiber diameter of 1.5 μm or less, and a step of fixing a pigment to the freshly water-treated fiber sheet with a binder. And a step of heating the fiber sheet to which the pigment is fixed with a binder at a temperature equal to or higher than the shrinkage temperature of the ultrafine fibers and equal to or lower than the melting point thereof. 8. The method for producing a colored fiber sheet according to claim 6 or 7, wherein the fiber bundle constituting the fiber sheet further includes ultrafine fibers having a fiber diameter of 1.5 μm to 4 μm. A method for producing a colored fiber sheet. 9. The method for producing a colored fiber sheet according to claim 6, wherein at least one of the ultrafine fibers and the ultrafine fibers is polypropylene. A method for manufacturing a colored fiber sheet. 10. The method for producing a colored fiber sheet according to claim 8, wherein the ultrafine fibers are polypropylene and the ultrafine fibers are polyamide. . 11. The method for producing a fiber sheet according to claim 6, wherein at least one of the ultrafine fiber and the ultrafine fiber is a primary fiber. A method for producing a colored fiber sheet.