JP2001226880A - Method for producing napped fiber sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a leatherlike sheet more excellent in antisoiling property, deodorant property and dye-affinity and having sufficient mechanical strength. SOLUTION: This method for producing a napped fiber sheet is characterized by performing step (1) and then performing (2) to (5) steps at random sequence. (1) a step wherein a paper web (A) obtained from a wet process and comprising an ultrafine fiber or a fiber capable of forming the ultrafine fiber or a dry web (B) comprising the above mentioned fibers and a textile (C) comprising a fiber having 10-30% shrinkage percentage in 90 deg.C hot water are superposed on each other and are interlaced to obtain an substantially and interlacingly integrated product, (2) a step wherein the surface of the (A) side or the (B) side of the interlacingly integrated product is napped, (3) a step wherein fiber is made into ultrafine fiber if the fiber is a fiber capable of forming the ultra fine fiber, (4) a step wherein the interlacingly integrated product is heat-treated to be shrunk by >=10% or more per unit surface, (5) a step wherein an elastic polymer is imparted to the intetlacingly integrated product by <=10 wt.% per the product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a nap fiber sheet which is highly excellent in antifouling property, odor preventing property and dyeing property.

[0002]

2. Description of the Related Art Conventionally, polyester fibers and nylon materials have been widely used as fibers constituting a napped fiber sheet because of excellent dyeing properties and mechanical properties.
These leather-like sheets have the drawback that dirt due to oil, mud, soy sauce, etc. is difficult to remove and odor tends to adhere. In addition, the nap fiber sheet made of polyester fibers also has a drawback in that the texture is harder than that of nylon fibers due to its physical properties, and there is a need for a nap fiber sheet having a soft texture.

Japanese Unexamined Patent Publication (Kokai) No. 2000-17580 proposes a nap fiber sheet for improving the performance described above, which uses an ethylene-vinyl alcohol copolymer fiber. The entangled non-woven fabric is impregnated with a large amount of an elastic polymer, and the nap fiber sheet is manufactured, so that the antifouling property, the odor preventing property, etc. are higher than the intrinsic ability of the ethylene-vinyl alcohol copolymer fiber. Is declining. In addition, since the fluff density of the ethylene-vinyl alcohol copolymer fiber in the surface layer is low, there is no sense of fulfillment as a nap fiber sheet, and the dyeing property does not result in a deep color because of a large amount of an elastic polymer present. there were.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to reduce the amount of an elastic polymer to be contained by entanglement and shrinkage treatment of an ultrafine fiber of an ethylene-vinyl alcohol copolymer and a heat-shrinkable woven or knitted fabric. As a result, by fully exhibiting the characteristics of the ethylene-vinyl alcohol-based copolymer fiber, the above-mentioned problems are to be solved, that is, antifouling properties and odor prevention properties, and further excellent dyeing properties. An object of the present invention is to provide a method for producing a leather-like sheet having sufficient strength to add.

[0005]

That is, the present invention provides a raised fiber sheet characterized in that the following steps (1) are performed, and then the steps (2) to (5) are performed in an arbitrary order. It is a manufacturing method of. (1) From an ultrafine fiber having an ethylene content of 25 to 70 mol% and having a single fiber fineness of 0.5 decitex or less or a short fiber containing the ultrafine fiber-forming fiber as a main fiber. The wet-processed papermaking web (A) or the dry web (B) made of the same short fibers and the woven / knitted fabric (C) made of fibers having a shrinkage of 10 to 30% in hot water at 90 ° C. Together
(2) a step of raising the surface on the (A) or (B) side of the entangled integrated product by performing an entanglement treatment; When the constituent fibers are ultrafine fiber-forming fibers, the step of making the fibers ultrafine is performed.
(5) 10% by weight of an elastic polymer with respect to the entangled integrated product
The process of applying below

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the fiber made of an ethylene-vinyl alcohol copolymer must be 0.5 dtex or less. Preferably it is 0.3 decitex or less, more preferably 0.1 decitex or less. When the main component of the ultrafine fibers exceeds 0.5 decitex, the appearance is deteriorated when the suede tone is adjusted, and the softness and the touch are also deteriorated.

In the present invention, as a polymer forming the ultrafine fibers, an ethylene-vinyl alcohol copolymer is used in terms of antifouling property and odor prevention property.
The vinyl alcohol-based copolymer is obtained by saponifying an ethylene-vinyl acetate-based copolymer. The amount of ethylene contained in the copolymer is 25 to 70 mol%. When the ethylene content of the copolymer is less than 25 mol%, the heat resistance decreases, and when the fiber is formed, the copolymer gels, the spinnability and the stretchability are reduced, and the obtained leather-like sheet is obtained. The texture becomes hard. When the ethylene content of the copolymer exceeds 70 mol%, the number of hydroxyl groups decreases, and the desired texture, antifouling property and odor prevention cannot be obtained.

As described above, an ethylene-vinyl alcohol copolymer is obtained by saponifying a copolymer of ethylene and vinyl acetate with sodium hydroxide or the like.
The degree of saponification is preferably 95% or more. If the saponification degree is too low, not only the crystallinity of the copolymer is reduced and the fiber properties such as strength are reduced, but also the copolymer is easily softened, and a trouble occurs in a processing step. In some cases, the texture of the leather-like sheet obtained with the above may be deteriorated.

The ethylene-vinyl copolymer according to the present invention can be produced by a known method. For example, ethylene and vinyl acetate are radically polymerized in a polymerization solvent such as methanol in the presence of a radical polymerization catalyst, then unreacted monomers are expelled, a saponification reaction is caused by sodium hydroxide, and an ethylene-vinyl alcohol copolymer is formed. After merging, pelletize in water, wash with water and dry. If an alkali metal is present in the process, the copolymer is liable to be thermally decomposed. Therefore, it is preferable to use a washing method in which the pellets are further washed with pure water containing acetic acid and then further washed only with pure water.

[0010] If necessary, 0.1 to 5 wt% of fine particles having an average particle diameter of 100 mm or less can be added to the ethylene-vinyl alcohol-based copolymer during or after polymerization. The material of the fine particles is not particularly limited. For example, silica gel (colloidal silica), dry silica, dry silica containing aluminum oxide, an alkyl group on the particle surface, and a silanol group on the particle surface are used. Inactive fine particles such as closed dry silica, alumina sol (colloidal alumina), fine particle alumina, fine particle titanium oxide, calcium carbonate sol (colloidal calcium carbonate), and internally precipitated fine particles in which a phosphorus compound and a metal compound are precipitated are preferable. Examples can be given. In particular, the average particle size is 15 to 70
Millimicron silica fine particles are preferable, and spinnability and stretchability are improved, and irregularities are obtained on the fiber surface, and the color of the leather-like sheet after dyeing becomes deeper and the sharpness is also improved.

Specifically, the leather-like sheet of the present invention is obtained, for example, by sequentially performing the following steps. (1-1) a step of producing sea-island structural fibers in which the island component is an ethylene-vinyl alcohol copolymer; (1-2) a wet method papermaking web (A) or a dry web (B) comprising short fibers of the fibers. (1-3) A step of superposing the web and the shrinkable woven / knitted fabric together to form an entangled and unified product (2) A process of raising the surface of the entangled and unified product on the (A) or (B) side (3) A) a step of removing the sea component polymer from the sea-island structural fiber to modify the fiber into an ultrafine fiber; (4) a step of shrinking the woven and knitted fabric integrally entangled; (5) impregnating the entangled nonwoven fabric with an elastic resin liquid; Step of forming an entangled nonwoven fabric filled with a dense porous body made of an elastic resin by coagulation (6) Step of dyeing with a dye In the above steps (2) to (5), the steps may be reversed if necessary. Or two steps It may be carried out at the time.

The present invention will be described below in the order of the above steps. First, the ultrafine fiber forming fiber used in the present invention, preferably the sea-island structure fiber, is obtained by mixing the ethylene-vinyl alcohol-based copolymer obtained as described above with one or more kinds having low compatibility with the copolymer. And mixed spinning with a thermoplastic polymer.

The polymer of the sea component preferably has a lower melt viscosity than the ethylene-vinyl alcohol copolymer under spinning conditions. Further, the ethylene-vinyl alcohol copolymer must be different in solubility or decomposability from a solvent or a decomposer (having higher solubility or decomposability than the ethylene-vinyl alcohol copolymer). Furthermore, it is a polymer having low compatibility with the ethylene-vinyl alcohol copolymer. Examples of such polymers include at least one polymer selected from polymers such as polyethylene, polystyrene, copolymerized polyethylene, modified polyesters represented by copolymerized polyesters, and thermoplastic polyvinyl alcohol. In particular, polystyrene can be easily extracted with tricrene, and polyethylene can be easily extracted with heated toluene.Modified polyesters such as sodium sulfoisophthalate copolymerized polyethylene terephthalate can be easily decomposed and removed with alkali, and thermoplastic polyvinyl alcohol can be decomposed and removed with hot water. For these reasons, these polymers are preferred. By extracting or decomposing and removing the sea component polymer from the sea-island structure fiber, the sea-island structure fiber can be made into an ultrafine fiber. In the present invention, the sea-island structural fiber may be such that, in the cross section of the fiber, the sea component may be divided into a plurality of portions by the island component polymer. Or a fiber in which the island component has a core-sheath structure. The island component polymer may be connected endlessly in the fiber length direction or may be in a discontinuous state extending in the fiber length direction. In the present invention,
The island component polymer needs to have a thickness of 0.5 decitex or less.

The raw spun yarn is subjected to stretching once or without being wound, and the stretching is performed by hot stretching using a hot air oven or a hot water bath. Usually 50-100 ° C
0.55 times or more and 0.9 times or more of the stretching ratio in the hot water bath.
The film is stretched at a stretching ratio of 5 times or less, preferably 0.70 times or more. If the stretching ratio is less than 0.55 times the cutting stretching ratio, a leather-like sheet having sufficient strength cannot be obtained.

The fiber length of the ethylene-vinyl alcohol-based copolymer fiber used in the present invention is not particularly limited, but it is preferable to select a suitable treatment method according to the length. As described later, for example, when the fiber length is 1 mm or more and 20 mm or less, it is preferable to form a web by a wet papermaking method, and when the fiber length is 20 mm or more and 100 mm or less, a method of forming a dry web by a card method or the like which is a dry method is used. It is preferably used.

In the present invention, when the fiber length is 20 mm or less, it is preferable to form the web by a wet papermaking method as described above. In particular, in the present invention, it is desirable to form a web by a wet papermaking method because it is excellent in terms of web uniformity. When the wet papermaking method is employed, it may be carried out according to a usual wet papermaking method. In the wet papermaking, for example, a slurry containing the above-mentioned sea-island structure fiber is defibrated by a known means,
The paper is made, and the fiber concentration in the slurry is about 1 to 1.
It is diluted to about 10% by weight, further diluted with a chest to 0.5 to 5% by weight, and made up by a paper machine. The net used may be a circular net or a short net, and the dryer is preferably a Yankee type, but may be a multi-cylinder type or a through dryer type, and the drying temperature is 80 to 80 which is the drying temperature in a normal paper making process. It may be performed at 130 ° C.

The compounding by the wet method is preferably composed of the ultrafine fiber forming fiber (a) composed of the ethylene-vinyl alcohol copolymer and the binder fiber (b), and the weight ratio (a) / (B) is 98/2 to 70/3
0 is particularly preferable, and 95/5 to 90/1 is more preferable.
0. The slurry may contain fibers other than the fiber (a) and the binder fiber (b). When the weight ratio of the (a) fiber is less than 70% with respect to the total amount of the fiber and (b), the fiber entanglement at the time of wet-type water entanglement is reduced, and
If it exceeds 8%, the tensile strength as a wet web is reduced, and web breakage may occur during the process. When the fiber length is less than 1 mm, the fibers are not easily entangled due to the water flow treatment after papermaking, and cannot be used. Also, 20m
If it exceeds m, the dispersibility during wet papermaking is poor, making the production of papermaking base paper difficult, and it cannot be used again.

Other fibers used besides the ethylene-vinyl alcohol copolymer fiber may be variously selected depending on the purpose, and are not limited, as long as they are fibers usable for wet papermaking. As the binder fiber (b) used in this wet method, polyvinyl alcohol-based binder fibers and polyester-based binder fibers used in papermaking can be used, but not limited to these. The basis weight of the web obtained by the wet method is preferably in the range of 10 to ²⁰⁰ g / m ² .

Next, the case where the napped fiber sheet of the present invention is produced via a dry method will be exemplified. When the fiber length is 20 to 100 mm as described above, a dry web may be formed by a card method, which is a dry method. The card method is, for example, a parallel card obtained by cutting the above-mentioned ethylene-vinyl alcohol-based copolymer fiber to a fiber length of about 50 mm,
This is a method in which the single fibers are oriented by a random card machine or the like, and if necessary, laminated using a cross wrapper to produce a dry web. The fiber length is preferably 30 to 6
0 mm. If the fiber length is less than 20 mm, it is difficult to cover a normal card, and it is difficult to obtain a desired raised fiber sheet. If the fiber length exceeds 100 mm, it is difficult to form a dry web, and it is difficult to obtain the desired raised fiber sheet. A suitable basis weight as a dry web is in the range of ^{20 to} 1000 g / m ² , and a fabric having twice the required basis weight is prepared, and is integrated in a thickness direction at an appropriate stage after being integrated with a woven or knitted fabric described later. Can be divided into two.

Subsequently, the web produced by the above-mentioned wet method or dry method and a woven or knitted fabric (C) composed of fibers having a shrinkage of 10 to 30% in hot water at 90 ° C. are overlapped and entangled. By performing the treatment, a substantially confounded integrated product of both is produced.

Here, a base fabric (C) for entanglement of the web must be used. A sheet consisting of the web alone has low strength and abrasion, and has a sufficient fluff density as a nap fiber sheet. Cannot be obtained.

The fibers constituting the woven or knitted fabric (C) used as the base fabric of the napped fiber sheet in the present invention must have a shrinkage of 10 to 30% in hot water at 90 ° C. As long as the fiber has such a hot water shrinkage, the fiber may or may not be modified, but in order to impart the above-described shrinkage to the fiber in hot water at 90 ° C., it is preferable to use a polyester fiber. And, for example, those in which an amorphous substituent such as isophthalic acid is introduced, or in which the crystallinity of the fiber is controlled by adjusting the melt viscosity, spinning, drawing and heat treatment conditions of the polyester even if it is not modified. Is used. Among the many fibers, polyester fibers are most preferable because fibers having the most desired shrinkage ratio can be easily obtained, and the shrinkage ratio is stable. The shrinkage of the fibers constituting the woven or knitted fabric is 10%
-30%, preferably 15-30%
Range. If the shrinkage of the fibers is less than 10%, the shrinkage of the fabric will be insufficient in the case of a woven or knitted fabric. On the other hand, if it exceeds 30%, the fabric is hardened due to the thickening of the fibers due to shrinkage, or the physical properties of the fabric are degraded due to the embrittlement of the constituent resin, and the physical properties are no longer useful.

As described above, the polymer used for the fibers constituting the woven or knitted fabric is, as described above, easy to control the shrinkage by heat, good color development at the time of dyeing, good performance against fastness, and general-purpose and inexpensive. In view of the above, polyester, that is, polyethylene terephthalate is desirable.
Of course, other than polyester, for example, nylon fiber,
Vinylon-based fibers, polyolefin-based fibers, acrylic fibers, and the like can also be used.

The fibers constituting the woven or knitted fabric preferably have a single fiber fineness of 0.1 to 2.5 denier. If the thickness of the single fiber is within this range, the sheet strength is not too large even after heat shrinking after spinning or after forming the fabric, and the sheet can be made excellent without becoming too hard.

The woven or knitted fabric used in the method of the present invention is preferably composed of spun yarn. As the spun yarn, a twist number capable of spinning within a range where the twist number during spinning does not exceed 900 T / m is preferable. In addition to the fact that the number of twists becomes extremely large, the spun yarn constituent fibers are also likely to become brittle due to shrinkage, and the apparent fiber density, tensile strength, etc. of the shrinkable sheet formed into a laminate with the web after being made into a fabric are Although improved, a cured sheet having a low tear strength is not preferred. Furthermore, a spun yarn having a twist number of 900 T / m or less is preferable for the present invention in terms of both yarn damage and entanglement with the fiber web. On the other hand, if the number of twists of the yarn is too high, the number of fluffs on the surface of the spun yarn is reduced, and the yarn is too tight, so that there is no looseness between the single fibers.
Entanglement with the papermaking web, and particularly when laminating with a papermaking web, fiber loss increases. However, if the twist number is 900 T / m or less, the entanglement of the web with the fluff peculiar to the spun yarn works effectively, and the loosened portion of the spun yarn also exists moderately. There is a phenomenon that the entanglement between the fiber and the woven or knitted fabric (C) becomes effective. In particular, in the case of papermaking webs, this effect can eliminate the dropout of web fibers, which is a drawback when the woven or knitted fabric (C) is a filament fabric. From these points, the use of spun yarn, 90
It is preferable for the present invention that the number of twists is 0 T / m or less. In the case of a spun yarn, the heat shrinkage of the yarn can be adjusted by adjusting the blending conditions with different types of fibers having different shrinkages. Therefore, the use of the spun yarn is useful in this sense.
The basis weight of the woven or knitted fabric (C) is 50 to 300 g / m ^2.
Is preferable.

Next, regarding the entanglement treatment, generally a non-woven fabric is used.
Can be implemented using the method used to manufacture
For example, confounding integration by fluid jet, needle
But the method is not limited to these.
Instead, a suitable method may be appropriately selected. But within that
It is particularly preferable to perform entanglement by water jet.
This hydroentanglement process is compatible with wet papermaking web and latent shrinkage.
A certain knitted fabric is laminated and 10 Kg by a high pressure water entanglement device.
/ Cm^TwoApplying the above high-pressure water flow to the laminated sheet
It is preferable to perform more sufficient entanglement. Water pressure of water entanglement
Is 10 kg / cm ^TwoIf the value is less than
The nap fiber density of the obtained nap fiber sheet is low due to sufficient
Disadvantages such as reduced wear resistance
You.

The nozzle for jetting a water stream preferably has a hole diameter of 0.15 to 0.7 mm, and more preferably 0.15 to 0.7 mm.
The one having a thickness of 0.5 mm is more preferable.

The drying after the treatment is preferably a multi-cylinder type or a through dryer type, but may be a Yankee type. The drying temperature is preferably from 80 ° C to 130 ° C. In the case of the wet method, an integrated facility for papermaking-water entanglement that does not require a drying step after papermaking is possible, and since there is almost no adhesion between the fibers, the entanglement of the fibers by the water flow is sufficiently exhibited. Suitable as a manufacturing method. On the other hand, in the needle punch method, the entanglement is sufficient, but the woven or knitted fabric may be damaged by the needle and the necessary tensile strength may not be obtained. However, this point can be improved, and in the present invention, although this means is not excluded, a manufacturing method using a confounding treatment method using a water flow is preferable.

The eyes of the entangled integrated product thus obtained
100-300 g / m ^TwoThe degree is soft
It is preferable because a certain sheet-like structure can be obtained.

Next, the entangled fiber sheet is treated with a chemical which is a non-solvent for the island component polymer and the woven or knitted fabric and is a solvent for the sea component polymer or a decomposer to convert the sea-island structure fiber into ultrafine fibers. I do. In the present invention, the fineness of the ultrafine fiber formed by removing the sea component from the sea-island structure fiber must be 0.5 decitex or less. Preferably it is 0.3 decitex or less, more preferably 0.1 decitex or less. If the main component of the ultrafine fibers exceeds 0.5 decitex, the appearance becomes poor when the suede tone is obtained, and the softness and the touch also deteriorate. In addition, although a method of manufacturing a web using ultrafine fibers obtained by removing the sea component may be used, a method of removing the sea component after confounding and making the web ultrafine is preferable from the viewpoint of the manufacturing process.

As the post-processing, the raised fiber sheet surface is raised to improve the surface quality. Examples of the treatment method include sanding treatment, which is generally performed for raising and surface finishing of suede-like, and surface finishing treatment with nylon or urethane coated fabric. For example, sanding conditions are as short as 20 mm or less, so it is preferable to set a sanding paper finer than No. 180 in a buffing machine, for example. The raising process may be performed at any step after the hydroentanglement process.

The raised fiber sheet obtained by the above-mentioned method or the like is then subjected to a heat shrink treatment to shrink it by 10% or more per unit area, whereby the web fiber and the woven / knitted fabric (C) are shrunk.
Entanglement with the napkin, and a further improved fluff density enhances a sense of fulfillment, improves abrasion resistance, and provides a raised fiber sheet that can be used for interiors, clothing, and the like.
As a specific shrinkage treatment method, treatment is performed in a hot water bath at 95 ° C. or lower. When treated in hot water exceeding 95 ° C., the ethylene-vinyl polymer melts. Therefore, 60-95 ° C
And the sheet area shrinks by 10% or more per unit area. Preferably, the shrinkage is 20% or more and 50% or less. Shrinkage in hot water is 10% per unit area
When the ratio is less than the above, the raised fibers are not sufficiently held between the woven and knitted fabrics (C) in the sheet, and the fiber sheet has low surface abrasion resistance, and a satisfactory feeling of surface raising cannot be obtained. On the other hand, when the shrinkage exceeds 50%, the fluff density becomes excessive and the nap fiber sheet may be distorted and may not be a uniform product.

As described above, the raised fiber sheet has a natural suede-like performance because the feeling of fulfillment is improved by the shrinkage treatment, and it can be put to practical use as it is. Is effective, for example, an elastic polymer such as polyurethane can be impregnated on one side or applied. In addition, a nap fiber sheet suitable for reversible clothing using the elastic polymer as a core material and nap fibers on both sides can be obtained. The weight of the elastic polymer used in this case is not preferable if used in a large amount as in the case of conventional artificial leather, because the sheet properties are rather deteriorated. It is used in an amount of 10% by weight or less, preferably 2 to 8% by weight, based on the sheet weight.

The elastic polymer used is, for example, at least one polymer diol selected from diols such as polyester diols, polyether diols and polycarbonate diols having an average molecular weight of 500 to 3,000, and complex diols such as polyester polyether diols. And at least one diisocyanate selected from aromatic, alicyclic, and aliphatic diisocyanates such as 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate; and ethylene glycol, isophorone diamine, and the like. And a modified product thereof obtained by reacting at least one kind of low-molecular compound having two or more active hydrogen atoms at a predetermined molar ratio. Elastic polymers such as elastomers, hydrogenated styrene-isoprene block copolymers, and acrylic resins are also included. Further, a polymer composition obtained by mixing these may be used. The elastic polymer is impregnated in a solution state or an emulsion state, and is solidified by a wet coagulation method or a dry coagulation method.

The nap fiber sheet thus obtained can be dyed more sharply by dyeing with a normal slen dye, and the obtained dyed article is excellent in light fastness and rub fastness. It will be.

Further, the post-processing treatment applied to general artificial leather as well as the napped fiber sheet of the present invention can be carried out. For example, it may be sheared or fir-processed to align the hair, and various other desirable steps may be added. For example, by acetalizing an ethylene-vinyl alcohol copolymer constituting ultrafine fibers with a monoaldehyde compound represented by formalin or a dialdehyde compound such as glutaraldehyde or 1,9-nonanedialdehyde or an acetalized product thereof. It is also possible to provide hot water resistance.

In the present invention, as a method of measuring the deep chromaticity (K / S), the spectral reflectance (R) is measured using a color analyzer (automatic recording type spectrophotometer, Model C-2000, manufactured by Hitachi, Ltd.). The following equation (Kubelka-Mun) was measured.
k). The greater this value, the greater the deep chromaticity. K / S = (1-R) ** / 2 / 2R (R is the reflectance at the position of the maximum absorption wavelength in the visible portion reflectance curve of the sample.)

According to the method for measuring the adhesion of deodorant according to the present invention, a container containing a sample cut into a 10 cm square was placed in a container.
After the odor (gas) of ppm was added and left at room temperature for 2 hours, the residual gas concentration (C1 ppm) in the container was measured. Subsequently, the gas was degassed from the container containing the sample, and the gas concentration (C) after heating at 60 ° C. for 30 minutes in 3 liters of nitrogen.
2 ppm). Further, the residual gas concentrations measured when no sample was placed were C1b and C2b, respectively, and the concentration of gas adhering to the sample at room temperature (C1b-C1) was 6%.
Attachment gas concentration at 0 ° C (C1b + C2b-C1-C
The deodorant adhesion was examined in 2). As the odor, ammonia (reagent first grade: manufactured by Wako Pure Chemical Industries, Ltd.) and acetic acid (reagent first grade: manufactured by Wako Pure Chemical Industries, Ltd.) were used.

As a method for measuring the antifouling property, a sample cut into a 10 cm square was subjected to 2 to 2 of each of the following dirt taken on a spoid.
After dropping 3 drops and leaving for 1 hour, wash test JIS1
Wash according to 0127-1, and after drying, make a grade judgment (5
Grade: no dirt remained, first grade: no dirt was removed). The following were used for each stain. Coffee: Nescafé Gold Blend (Nestlé Japan Co., Ltd.) Curry: House Java Curry (House Foods Co., Ltd.)
Stewed with beef, onion, carrot, and potato. Ink: Water-based black ink (manufactured by Sailor Fountain Pen Co., Ltd.) Dirty oil: Motor oil plus 0.1% carbon. Lipstick: Elixir Fine Rouge RD430 (made by Shiseido Co., Ltd.) White: Elixir Smileish Powdery Pact Oakle 20 (made by Shiseido Co., Ltd.)

As a method for measuring wear resistance, JIS-L
Evaluation was performed using a Martindale abrasion tester according to 1069.

In the present invention, the shrinkage ratio of the fiber in hot water at 90 ° C. is the length measured under a load of 1/500 g / dr applied to the fiber and the free state in warm water at 90 ° C. for 5 minutes. It is obtained from the difference from the length measured under a load of 1/500 g / dr again after immersion and air drying.

[0042]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. The measured values and evaluation methods shown in the examples and comparative examples are as described above.

Example 1 Using methanol as a polymerization catalyst and azobisisobutyronitrile as a polymerization initiator, ethylene and vinyl acetate were subjected to radical polymerization at 60 ° C. under pressure to give an ethylene content of 44. A mole% of ethylene / vinyl acetate copolymer was prepared. Next, the ethylene / vinyl acetate copolymer is subjected to a saponification treatment in a methanol solution containing caustic soda, and washing is repeated using a large excess amount of pure water to which a small amount of acetic acid is added. The washing with pure water was repeated. Then, after water was separated from the copolymer by a dehydrator, it was sufficiently dried by vacuum drying at a temperature of 100 ° C. or less. The obtained ethylene / vinyl alcohol copolymer had a saponification degree of 99.5 mol% and a melt index (19).
(0 ° C, under a load of 2160 g) was 5.5 g / 10 min, and the melting point was 160 ° C.

The ethylene / vinyl alcohol-based copolymer obtained above was used as an island component, and a composite spun fiber of 16 islands (sea-island ratio of 1: 1) using a modified polyester as a sea component was obtained by a melt spinning method. Was stretched and cut into a length of 3 mm to obtain a staple having a thickness of 3 dtex. The obtained staple was used as a main fiber, and a polyvinyl alcohol-based fiber was mixed as a water-soluble binder fiber so as to have a weight ratio of 95/5, and dispersed in water to obtain a 1% concentration slurry solution. Further, it was diluted with a chest to 0.5% by weight, made up by a paper machine, and the formed wet paper was removed by vacuum dehydration to remove excess water, transferred to a Yankee type dryer, and heated to 90 ° C. To obtain a wet web having a basis weight of 40 g / m ² . Next, the shrinkage in hot water at 90 ° C. is 15
% Made of raw cotton consisting of modified polyester,
A plain woven fabric made of a spun yarn having a twist number of 800 T / m is used as an intermediate layer, and the upper and lower portions are covered with the wet web, and the laminate is provided with a nozzle diameter of 0.10 mm, a nozzle pitch of 1 mm,
20Kg / cm ² , 30Kg / c from one row of nozzles
fibers were woven entangled by injecting a columnar flow of water pressure in m ^2. The distance between the nozzle and the laminate was 30 mm, and a stainless steel 80 mesh wire mesh was used as a support member below the laminate, and suction dehydration was performed through the wire mesh. The same treatment was applied to the surface opposite to the sheet surface from which the columnar flow was jetted. In order to raise the surface of the entangled sheet thus obtained, the surface of the nap fiber is sanded with a compact buffing machine (using a paper file No. 400) to raise the surface.
At a concentration of 60 g / liter in an aqueous solution of NaOH to decompose and remove the modified polyester which is a sea component in the conjugate spun fibers, at the same time 23% in sheet vertical direction and 2 in horizontal direction
After 2% shrinkage treatment, washing with water and drying at 100 ° C.
Further, the polyurethane was fixed so as to have an adhesion amount of about 5% to the sheet, and then dyed with a slen dye. Further, the surface of the nap fiber was subjected to a hair styling treatment to obtain a suede-like nap sheet. Table 1 shows the physical properties.

Example 2 After crimping the conjugate spun fiber of Example 1, the fiber length was 5
It is cut to 1 mm, a card having a dry weight of 120 g / m ² is prepared using a card and a cross wrapper, and after laminating the web and the plain woven base fabric described in Example 1, water pressure is 40 kg by water entanglement. / Cm ² entanglement treatment. Thereafter, the same treatment as in Example 1 was performed, and a nap fiber sheet having excellent mechanical properties, stain resistance, and odor resistance was obtained. The physical properties are shown in Table 1.

Comparative Example 1 The composite spun fiber of Example 1 was cut to a fiber length of 51 mm to produce a web using a dry card or cross wrapper, and the web was subsequently entangled with a needle punch machine. Was. After the polyurethane was attached to this entangled nonwoven fabric, a weight reduction treatment was performed with an alkali solution. The polyurethane was fixed at 35% by weight to the sheet. After that,
When the treatment was carried out in the same manner as in Example 1, the chromaticity was poor and the nap fiber sheet did not have satisfactory antifouling properties. The physical properties are shown in Table 1.

Comparative Example 2 A nap fiber sheet was obtained in the same manner as in Comparative Example 1, except that the amount of polyurethane fixed was 5% by weight based on the sheet. Although the color depth was sufficient, the amount of polyurethane adhered was small, so that the fiber was not easily caught and slipped off easily, resulting in a sheet with many fluffs and poor abrasion resistance.

Comparative Example 3 The treatment was carried out in the same manner as in Example 1 except that the woven or knitted fabric was not used. As a result, the fiber web was disturbed by the water flow at the time of entanglement, and the sheet could not be formed.

Comparative Example 4 In Example 1, 6 nylon (manufactured by Ube Industries, Ltd.) was used in place of the ethylene-vinyl alcohol copolymer, and only the dyeing was changed to the gold-containing complex dye. A raised fiber sheet was obtained, but it was recognized that the obtained sheet had poor antifouling resistance and odor resistance. The physical properties are shown in Table 1.

Comparative Example 5 A wet sheet was prepared in the same manner as in Example 1, and a woven fabric made of non-shrinkable raw cotton (shrinkage ratio by hot water treatment: 3%) was used in the same manner as in Example 1. A raised fiber sheet was obtained, but the obtained sheet had a lot of fluff and poor abrasion resistance.

[0051]

[Table 1]

[0052]

The raised fiber sheet of the present invention minimizes the amount of the elastic polymer by the strong entanglement of the woven or knitted fabric and the ultrafine short fibers of ethylene-vinyl alcohol copolymer having excellent physical properties. This makes it possible to obtain a nap fiber sheet having excellent color tone, stain resistance and odor resistance. Due to such characteristics, it is extremely suitable as a material for a substitute for a cloth product suitably used for interiors and clothing.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F055 AA02 BA11 CA16 DA07 EA07 EA12 EA22 EA24 EA25 EA28 EA34 EA36 FA15 HA04 HA14 HA22

Claims (5)

[Claims] 1. A method for producing a napped fiber sheet, comprising the steps of: (1) performing the following step (1) and then performing the steps (2) to (5) in an arbitrary order. (1) From an ultrafine fiber having an ethylene content of 25 to 70 mol% and having a single fiber fineness of 0.5 decitex or less or a short fiber containing the ultrafine fiber-forming fiber as a main fiber. The wet-processed papermaking web (A) or the dry web (B) made of the same short fibers and the woven / knitted fabric (C) made of fibers having a shrinkage of 10 to 30% in hot water at 90 ° C. Together
(2) a step of raising the surface on the (A) or (B) side of the entangled integrated product by performing an entanglement treatment; When the constituent fibers are ultrafine fiber-forming fibers, the step of making the fibers ultrafine is performed.
(5) 10% by weight of an elastic polymer with respect to the entangled integrated product
The process of applying below 2. A method for dyeing a napped fiber sheet, comprising dyeing the napped fiber sheet according to claim 1 with a slen dye. 3. A method for producing a napped fiber sheet, comprising subjecting an ultrafine fiber comprising an ethylene-vinyl alcohol copolymer contained in the napped fiber sheet according to claim 1 to acetalization to carry out a crosslinking treatment. 4. The method for producing a napped fiber sheet according to claim 1, wherein the woven or knitted fabric is made of a spun yarn having a twist of 900 T / m or less. 5. The method according to claim 1, wherein the shrinking treatment in the step (4) is performed in hot water at 95 ° C. or lower.