JPS6030376B2 - non-woven fiber structures - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a nonwoven fibrous structure and an artificial leather obtained from this nonwoven paper structure.

More specifically, it is a non-woven fabric in which the fiber east, which is a collection of ultra-fine single loose vertical lines and any number of these single wires, is three-dimensionally intertwined with a relatively coarse knitted fabric frame existing on the back side or the back side area. The present invention relates to a fiber structure and an artificial leather in which a rubber-like elastic body is interposed in the structure. It is generally known that deerskin-like artificial leather can be obtained by filling the fiber gaps of a nonwoven fabric made of ultrafine fibers with a rubber-like elastic material.

However, in the artificial leather to date, single fibers are intertwined, and the density of the nonwoven fabric is low. In order to increase the density and give a sense of fulfillment, it is necessary to increase the filling amount of the rubber-like elastic body. As a result, the obtained artificial leather becomes rubber-like. On the other hand, if the amount of rubber-like elastic material is reduced, the rubber-like feel will disappear, but the resulting artificial leather will only have a flimsy feel and no sense of fullness. Furthermore, when used for clothing, it is preferable that the thickness of the artificial leather be one leg or less; if it is thicker than this, flexibility (drapeability) will be lost, making it unsuitable for clothing.

Non-woven fabrics made of only a single fiber tend not to have high density, so they tend to have low strength when made into thin materials. In other words, the recovery rate is poor at locations that are subjected to strong bending, and in severe cases, they may break at those locations and fall off. In addition, knitted fabrics, stitches, etc. have the disadvantage of being easily torn when subjected to tearing stress. Furthermore, when the surface of artificial leather, which is made up of only intertwined fiber bundles, is raised, the fluff becomes the fluff of the fibers, and the raised condition is significantly rougher than that of natural leather, resulting in a poor surface texture. It has the disadvantage that it feels like cheap leather with a rough texture. The inventors of the present invention have finally completed the present invention as a result of intensive research to overcome the above-mentioned drawbacks.

The present invention is a structure consisting of fibers of various sizes and thicknesses, single fibers subdivided from the fibers, and knitted fabrics, and the wire fabrics are on the back side or rear side of this structure. A nonwoven fiber structure that exists in a castle and has an integral structure as a whole due to the three-dimensional mutual entanglement of fibers and single fibers, and the random entanglement of these into the texture of knitted fabrics. , and a leather-like material obtained by interposing a rubber-like elastic polymer in the interstitial spaces of this structure, and furthermore, a nubuck-like artificial leather obtained by brushing the surface of this leather-like material. It is.

The feature of the present invention is a short fiber non-woven fabric structure in which ultra-fine single fibers and fiber strands of various sizes, which are the whole structure of the single fibers, are intertwined three-dimensionally, and The castle is intertwined with knitted fabrics or woven fabrics to form a structure that is inseparably integrated.This makes it possible to obtain a leather-like material that has a sense of fulfillment and high strength, and also has various excellent physical properties. It shows.

Therefore, it is possible to provide a leather-like material with physical properties that could not be achieved with conventional nonwoven fabrics made only of single fibers or fibers.

In other words, the texture and strength of nonwoven fabrics, such as their fineness and flexibility, are
There is a close relationship with the density of the nonwoven fabric, and simply intertwining the fibers is not sufficient to obtain desirable strength and texture.

Not only the intertwining of the fiber east, but also the intertwining of the ultra-fine single fibers, the intertwining of the fiber east and the single fiber supply, and even the intertwining with the bran fabrics existing on the back side or the back side castle, etc., the density can be improved. A nonwoven fibrous structure with extremely high The nonwoven fiber structure of the present invention has such a very high-order entangled state, and as a result, it has a density comparable to that of natural leather (approximately 0.0 For the first time, we were able to obtain a leather-like material with strength as high as 0.4 pm/day).

Specifically, bending strength, sewing strength, and dimensional stability are physical properties that are naturally problematic for clothing products, but these values are based on the structure of the nonwoven fabric, that is, the fibers that make up the nonwoven fabric. It is related to the bonding state due to mutual entanglement, and it can be said that this is related to the difficulty of slipping through the fibers in the same length. Naturally, the resistance of fibers to slipping is greatly influenced by the length of the nonwoven fabric, that is, its density. Therefore, in general, in order to improve the strength and dimensional stability of a nonwoven fabric, it is most appropriate to increase the density of the nonwoven fabric. As mentioned above, the nonwoven fiber structure of the present invention includes not only fiber strands, but also single fibers subdivided from the fiber strands, and even whole woven fibers existing on the back surface or the back surface area. It is a non-woven fiber structure that is integrated in an extremely complex intertwined state, and its density is naturally much higher than that of the non-woven fabric made only by Senihigashi. is extremely good.

In terms of flexibility, Fiber East is considerably segmented into ultra-fine single fibers, making it more flexible than nonwoven fabric made only of Fiber East.

On the other hand, the coexistence of large 4-sized fibers with various thicknesses and single fibers also has a large effect on the fluff of the surface.

In other words, when a non-woven fiber structure is brushed, thin single-fiber fluffs are created between the fluffs of the fibers of various sizes, creating a smooth surface with an extremely high fluff density. can be produced. In particular, the leather-like material of the present invention has noticeable finely divided fibers and fluff of single fibers,
The surface texture is fine, and rather than suede-like (natural leather with a brushed surface on the flesh side), it is an artificial leather made of nubuck steel with a brushed surface on the silver side. As can be understood from the model structure of natural leather shown in FIG. 4, the thickness of the constituent fibers and fiber east becomes thinner as it approaches the grain side from the thick fiber east consisting of thick fibers on the flesh side.

Therefore, while suede leather has a coarse texture with the flesh side raised and the thick fibers on the east side raised, nubuck leather has a thin texture with the grain side raised and the thin fibers on the east side are fluffy. The non-woven fiber structure and leather-like fabric of the present invention have a downy appearance as shown in Fig. 1, in which fluff from finely divided fibers of various sizes and fluff and fluff from single fibers are mixed together. It covers the surface and has a generally nubuck-like surface, and is an extremely valuable nonwoven fiber structure and leather-like material.

In the nonwoven fiber structure of the present invention, the knitted fabric existing on the back surface or the back surface area effectively entangles the short fibers to stably form a delicate nonwoven structure with a higher density of short fibers. It plays an important role in making this possible.

This presence further improves the density of the nonwoven fiber structure,
At the same time, you will feel more fulfilled. Furthermore, it also contributes to increased strength and dimensional stability. In addition, since the knitted fabric is on the back side or in the back surface area, during the intertwining process of the nonwoven fabric, fibers and short fibers of single fibers may be inserted into the structure of the knitted fabric or become entangled, resulting in three-dimensional mutual interaction. This is because the intertwining becomes stronger. In other words, in order to make short fibers into non-woven fabrics, the fibers are crimped or adhesive is used to fix the fibers together to some extent, and based on this bonding force, new material is created using needle punching, etc. This creates a strong bond.

Since the fibers are intertwined, if they are not free, they will move in random directions and cannot be intertwined. However, if there is too much freedom, a strong entanglement will never occur. Therefore, when the intertwining process begins, one end or part of the short fibers is supported and fixed by something, and one free end or freely movable part becomes entangled with the freely movable part of another short fiber. The desirable mechanism of non-woven fabric is that the intertwining occurs one after another in a chain to form a three-dimensional intertwining. The striped fabrics present on the back surface or back surface area of the nonwoven fiber structure of the present invention move like a support for short fibers when this entanglement is gradually resolved, and prevent the fibers from slipping out. I won't let you wake up.

Since there is no slippage of the fibers, as they become entangled,
The three-dimensional intertwining of the nonwoven fabric becomes dense, and the density of the nonwoven fabric increases, resulting in a nonwoven fiber structure that is strong and substantial. Furthermore, the presence of striped fabrics plays a major role in facilitating the presence of longitudinally oriented (perpendicular to the sheet plane) fibers within the three-dimensional intertwined structure.

This is because the knitted fabric exists on the back side or in the back surface area, so when the fiber bundles and single fibers become entangled, they become entangled or entangled within the structure of the knitted fabric. Fibers that are inserted or entangled in knitted fabrics in this way,
The fibers remain vertically oriented or as single fibers, improving the compression ratio and compression recovery rate of the nonwoven fabric. As mentioned above, striped fabrics not only add their own strength to nonwoven fabrics, but also help the three-dimensional intertwining of the fibers and single fibers that make up the nonwoven fabric, and It facilitates the presence of fibers in the vertical direction and serves to significantly improve the physical properties of the nonwoven fiber structure of the present invention.

Fiber East has ultra-fine single fibers and various thicknesses,
Inserting into or penetrating the gaps in the structure of striped fabrics,
Alternatively, it indicates a state in which the object threads its way into the space.

In other words, it indicates a state in which the constituent fibers of the bran fabric, the ultrafine fiber bundle, and the single fiber strands are intertwined to such an extent that the fibers do not easily slip through. Of course, this also includes a situation in which the single fibers or fibers have once passed through knitted fabrics and been pushed back into the cotton fabrics. "Unseparable"
The nonwoven fiber structure of the present invention is not simply a laminate made of other nonwoven fabrics and knitted fabrics, but is also composed of bran fabrics, single fibers, and fibers. Peeling or separation from the intertwined parts can never occur. Furthermore, the single fibers and fibers are never planted in a substantially regular manner in striped fabrics such as flocked or tufted fabrics. Also, it is never attached to striped fabrics using adhesives or the like. Fibers and monofilaments can take random directions, and their contact points are also extremely random and tangled. In the nonwoven fiber structure of the present invention, the knitted ball is present on the back surface or the back surface area.

Here, the rhombus area refers to a position where the bran fabric can be seen and hidden, rather than being completely exposed on the back side.
The present inventors previously provided a nonwoven fabric belt structure in which a knitted fabric was inseparably integrated into an inner layer in Hakamafujisho 51-Nevus No. 6.

In contrast to this earlier application, the present invention is a structure in which knitted fabrics are integrated into the diamond side or back side area, but since the striped fabrics are present on the back side or face area, there are various points. It has different characteristics from that of the earlier application. First, a small amount of the nonwoven fabric portion consisting of the fibers and single fibers is sufficient.

This is extremely advantageous economically. That is, in order to obtain good artificial leather, ultrafine fibers are required, but these are expensive. Therefore, the current situation is to reduce costs by minimizing losses and increasing productivity as much as possible. On the other hand, the non-woven fiber structure of the present invention has the great advantage that it is possible to make the surface region of the ultra-fine fibers and the non-woven fabric portion of the single fibers thinner, and it is possible to suppress the consumption of expensive ultra-fine fibers. There is. At the same time, the processing process can be streamlined, and the number of man-hours in the non-woven process can be cut in half. Secondly, the properties of the striped fabrics present in the back area have a large influence.

In other words, in the case of mesh-like striped fabrics, the pattern appears even on the surface of the nonwoven fabric, making it slightly uneven, resulting in a leather-like material with a pattern. For example, if a knitted fabric with tortoise-shell stripes is used, the tortoise-shell pattern will stand out on the front, creating an embossed effect. This is thought to be a phenomenon that occurs because fibers and single fibers are inserted into the voids of striped fabrics, and the gaps are not compensated for. On the other hand, in the case of the nonwoven structure in which knitted fabrics are interposed in the inner layer region of the prior application, the fibers of the nonwoven fabric parts on both sides of the striped fabrics move toward each other, forming the stitches of the knitted fabrics. Since they cancel each other out, no pattern appears on the surface. Thirdly,
Since the striped fabric exists on the back surface or the back surface area, it is easy to adhere to other objects. Therefore, it is also suitable for interior surface materials. The purpose and features of the present invention have been explained above, and the present invention will now be specifically explained in detail with reference to the drawings.

The nonwoven fiber structure and leather-like material of the present invention have a cross-sectional structure as shown in FIG.

(The cross-sectional structure shown in Figure 1 is after the surface has been brushed, but there is virtually no change in the cross-sectional structure before the brushing process. Also, in Figures 2, 3, and 4, The same thing can be said.) In Fig. 1, [cross section of the striped weave structure of small line woven fabrics, 'W' is the east of the ultra-fine fibers, 'b'' is the fiber east that is finer than b, and c is the east of the fine fibers. Ultra-fine single fiber, d is fluff on the east side of the fiber, d
′ is the fluff of the finely divided fiber east, and e is the fluff of the single fiber.

For example, the following methods can be used to manufacture a fiber structure as shown in FIG. For example, when using copper ammonia rayon fiber as the fiber east, when spinning multifilament of steel ammonia rayon fiber, 0.5
Before the monofilament paper of denier or less is completely solidified, it is collected using a collection guide, and the single fibers are self-adhered to each other to form fibers of 5 to 25 fibers, preferably 1 or less. Cut to obtain short fibers.

The ultra-fine self-adhesive short fibers with a single yarn denier of 0.5 denier or less obtained in this way are made into paper sheets using a hydroformer type paper making machine, and then relatively coarse striped fabrics are made into paper sheets. It is spread on the back side of the sheet to obtain a two-layer laminated sheet product as shown in FIG.

A nonwoven fabric having a three-dimensional entangled structure is obtained from this laminated sheet by means of high-speed fluid flow (water jet ejected at high pressure from a narrow nozzle), needle punching, or the like. A considerable portion of the self-adhesive part of this nonwoven fabric has been peeled off, and it has been separated into thin fibers and even single stitches, which are intertwined with each other and form a three-dimensional structure with the knitted fabric on the back side. They intertwine with each other, resulting in a fiber structure as shown in Figure 1. The ultrafine fibers used in the present invention, which are aggregates of single fibers of 0.5 denier or less, can be obtained by various methods.

For example, a commonly known fiber cross section consisting of two components can be obtained by extracting the sea component from a so-called sea-island fiber that shows the relationship between the sea and islands. Alternatively, it can also be obtained by methods such as flash grade yarn. Furthermore, as shown above, it can also be obtained by extruding it in a very fine state into a medium such as water, like cellulose fibers. However, it is very difficult to obtain the product of the present invention by simply using ultra-fine fibers.

In other words, when forming into a sheet or using non-woven fabrics, Fiber East does not have bonding or binding force between single fibers, such as ultrafine Fiber East, which simply extracts sea components from Umejima fiber, or fibers obtained by flash spinning. During the process, the fibers break apart into single fibers, causing various problems in the manufacturing process. For example, when a carding machine is used, ultrafine fibers sink into the clothing, making it impossible to obtain a steady web and having a negative impact on yield. Furthermore, when making a paper sheet, the ultrafine fibers become entangled in the slurry chest, making it impossible to achieve a clean dispersion. Therefore, in order to obtain the product of the present invention, the fiber orientation is almost maintained during the sheeting process using a paper making machine or a card machine, and a high-pressure fluid flow or
It is best to use fibers in which the single fibers are joined together with such force that some or most of the fibers are fragmented and turned into single fibers in a three-dimensional entangling process such as needle punching. .

Therefore, in the case of sea-island fibers or ultra-fine fibers obtained by flash spinning, it is necessary to glue the fibers together in advance or lightly attach them to each other using high-temperature steam to create fibers with weak bonds. be. In addition, in the case of cellulose fibers, etc., before the single fibers are completely solidified in the threads, they are assembled using a binding guide, etc., and the single fibers are bonded together to form a self-adhesive fiber. This goal can be achieved.

The denier of the fiber east component single fiber must be 0.5 denier or less; if it becomes thicker than 0.5 denier, the soft, moist, leather-like texture will be lost.

In addition, the fuzz that stands up when the surface is brushed becomes stiff and clumpy, making it impossible to obtain a leather-like product with a good texture. The thickness of the fibers used is about 1 to 200 deniers,
The preferable range for clothing is about 2 to 60 deniers.

However, even if a somewhat thick denier fiber is used, it is advisable to vigorously subdivide it when making it into a non-woven fabric. In any case, the fiber structure of the present invention consists of fibers of various sizes and thicknesses, that is, fibers of various sizes with different numbers of single fiber bags, and the main body of Nuseiki-zukuri, which has a mixture of single fibers in which the fibers are subdivided. It was formed by As the polymer forming the ultrafine fibers used in the present invention, any organic polymer substance having fiber-forming ability can be used.

For example, any material such as cellulose, cellulose acetate, polyamide, polyester, polyacrylonitrile, polyethylene, polypropylene, or a copolymer thereof can be used. On the other hand, the knitted fabric existing on the back side or the back side of the fiber structure of the present invention has a roughness to the extent that the ultrafine fibers and ultrafine single fibers can be entangled or filled into the striped weave structure. It is necessary, and it is preferable to select a basis weight in the range of 10 to 100 y/m, and optimally 30 y/m to 70 y/m.

When it is less than 10 minutes, the form of the striped fabric becomes extremely loose, and when it is intertwined with fibers or single fibers on the back side or back side area, it is not spread out evenly and wrinkles occur.

In addition, it may be too thin to fix the fibers or single fibers in the vertical direction, making it impossible to improve the sense of fullness of the nonwoven fiber structure. In other words, its value as an inserted striped fabric is no longer recognized. On the other hand, when the basis weight exceeds 100/me, the striped weave structure becomes dense and entanglement, penetration, and filling of fibers and single fibers cannot occur, and they are entangled with the fibers of knitted fabrics. There is a tendency to be unable to create integrated structures. Therefore, in the case of fibers as shown in Figure 2, the single fibers do not intertwine with the knitted fabric, resulting in only a sheet-like product with a two-layer structure, which results in a leather-like product that lacks a sense of fulfillment and has low strength. . When the knitted fabric is intertwined with the fibers and single fibers of the nonwoven fabric layer, the texture of the fiber structure is significantly improved compared to the case of a two-layer structure sheet.

That is, in the case of a two-layer structure sheet as shown in FIG. 2, it is a fiber structure that is the sum of the textures of a nonwoven fabric and a knitted fabric, and has the drawbacks of each. On the other hand, the nonwoven fiber structure of the present invention creates a new texture that looks like a combination of each texture,
It is neither a knitted fabric nor a simple non-woven fabric, as it covers each other's shortcomings, giving it an extremely complex and unique texture. From the viewpoint of flexibility, it is better to select the constituent fibers of the armpit fabrics from multi-twill yarns not exceeding 70 deniers (single yarns are preferably 3 deniers or less). Regarding the types of knitted fabrics, there are various types of knitted fabrics such as weft knitting, vertical striped knitting represented by tricot knitting, sheath knitting, and various knitted fabrics based on these knitting methods, or plain weaving, twill weaving, satin weaving, and their spellings. There are various types of textiles, including textiles, which have surface stitches and textures that can be embedded within the tissue.
In addition, any type of material may be used as long as it has a textile structure that also maintains textile fiber voids inside. The fibers constituting the bran fabrics may be any fibers that can be knitted or woven, such as synthetic fibers such as polyester and bolyamide, and recycled cellulose fibers such as rayon and cupra, but if possible, the single yarn denier should be 3 deniers or less. preferable. This is because knitted fabrics with too large a single yarn denier may make the nonwoven fiber structure and the leather-like material obtained from this structure hard. It is preferable that the basis weight of the knitted fabric in the present invention does not exceed 70% by weight of the basis weight of the entire structure.

If it exceeds 7% by weight, the knitted fabric may be exposed on the surface of the nonwoven layer, or the elasticity unique to the nonwoven layer may be lost.

More preferably, the range is from 4% to 1% by weight.
The ratio of fiber east and subdivided single fibers is 2.
Preferably, the amount is less than or equal to % by weight.

If the mixing rate of single fibers is lower than 2% by weight, the nonwoven fabric will consist almost entirely of fibers, and the above-mentioned drawbacks will appear. When the state of the fibers constituting the non-woven structure of the present invention is observed by pulling out the fibers, there are monofilamentous, thick and thin fibers. It is thought that it forms a non-woven structure.

Determining the mixing ratio of fiber east and single fiber is difficult, and currently the only way is to judge it with the naked eye from an enlarged photo.

For example, a cross section of a nonwoven material is photographed at a magnification of 70 pm using a scanning electron microscope. Draw lines on this photo at two equal intervals vertically and horizontally, and color the areas occupied by single fibers red. After coloring, draw this photo according to the ruled lines at 2 skin corners 4.
Cut into pieces and separate into red-colored pieces and other pieces. Next, by measuring the weights of these two types of small pieces, the ratio between the weight of the fiber east and the weight of the single fiber is determined. This value is converted into a percentage and used as the mixed ratio of fiber east and single fiber. The number of samples was n:20, and the average value can indicate the mixing ratio of fibers and single fibers in the nonwoven fabric. The structure and internal entanglement of the fiber structure of the present invention have been explained above, and the ultrafine fibers and single fibers of various sizes and thicknesses are three-dimensionally intertwined and integrated with the green fabric. The structure has the appearance of a leather-like material with a soft leather-like texture and strength even as it is. When this surface is brushed, a fluffy mixture of downy fibers and single fibers is produced, resulting in a leather-like product with a nubuck-like surface. Furthermore, a better leather-like product can be obtained by impregnating the fiber structure with a rubber-like elastic polymer and interposing the elastic polymer between the fibers. That is, the voids in the fiber structure of the fiber structure are filled with a rubber-like elastic polymer, and the entire fiber material is bound. Next, when the surface of this sheet is brushed with sandpaper or a wire brush, a mixture of ultra-fine fiber fluff of various sizes and thickness and ultra-fine single fiber fluff is raised, and the grain side of the natural leather is brushed. Upon processing, a nubuck-like leather-like material was obtained. This leather-like material is an artificial leather having a cross-sectional structure shown in FIG. 1, in which rubber-like elastic bodies are dispersed in small spaces between fibers, and is a completely new structure. As mentioned above, the condition of the fluff covering the surface is an important requirement that determines its value as artificial leather. In other words, the softer (fine) the fluff and the higher the fluff density, the more likely it is that the leather-like product will have a feel similar to the highest quality natural leather, especially silver-faced suede leather (nubuck-like). As shown in Figure 8A, the downy fluff of the leather-like material of the present invention is not only composed of fibers, but also ultra-fine single fibers (fibers are also subdivided into fibers of various sizes and thicknesses). The fibers are often subdivided into very thin fibers.), and the density of the fluff is extremely high. The reason why the fluff of thin fibers and fluff of single fibers occurs and binds is because the internal structure of the nonwoven fabric has already formed a three-dimensional entanglement that includes not only fibers but also subdivided fibers and single fibers. This is because there is a three-dimensional entanglement of fibers, and this cannot happen with a simple three-dimensional entanglement of fibers. That is,
Actively subdividing the fibers and creating a mixture of finely divided fibers and single fibers not only improves the density of the nonwoven fabric and increases its strength and fullness, but also improves the surface It also has the effect of making the condition extremely smooth. Of course, the fluff exposed on the surface is continuous to the inside of the nonwoven fabric, and because the three-dimensional intertwined structure is dense, it is extremely difficult for the fluff to come off. On the other hand, the surface fuzz obtained from a nonwoven fabric consisting only of fiber bundles has a rough surface texture, with the thick fuzz on the east side of the fibers roughly protruding as shown in Figure 8. It leaves a feeling. The PU in Figure 8 A is a schematic representation of a rubber-like elastic body, and in reality it is more complex and is filled in the fiber voids in a spongy manner, but it is easy to understand. It is expressed in block form for ease of reference.

The present invention will be explained in more detail by giving Examples and Comparative Examples below.

However, the physical properties shown in the Examples and Comparative Examples are the values obtained by the following measurements.

The thickness is a value measured under a flow load of 100 mm/c. For tensile strength, take a sample of 20 skins in length x 1 skin in width, stretch and cut it using an autograph with the grip length set as 5 arcs at both ends, and find the maximum strength at that time.

To make a strong cut, take a sample as shown in Figure 6A and make a cut from one end to the other end to C. Next, as shown in Figure 6-2, the gripping length at the A and B ends was set to 5, and the A and B ends were pulled in the direction of the arrows, and the maximum force when point C was torn was measured using an autograph. It is. To measure the sewing strength, take two samples of length 1 ratio x width 2 arcs, stack these two samplers as shown in Figure 7A, and then overlap the overlapped part as shown in Figure 7. Sew in a U-shape. The sewing conditions are a normal sewing machine, and the needle is 1.
No. 1, sewing thread polyester thread No. 50, sewing stitch 1
2 needles/3 skins. These two samples were sewn together in the vertical direction, then pulled using an autograph while grasping the 5 forces on both sides of the L. The maximum strength when a break occurs at the seam (
k9). Divide the maximum strength by the seam (1. &ne) to obtain the sewing strength (k9/2). The flexibility is determined by JIS LI079-19665.1 column.

Softness Measurement was performed by method A (45o cantilever method). The numerical value indicates the sliding distance of the sample, and the smaller the value, the more flexible it is. To determine the elongation recovery rate, take a sample with a length of 2 ratios x width of 1 arc, grasp the upper end, and fix the sample by hanging it from above.

Next, the lower end 5 arcs are grasped, a load of 1.0k9 is suspended, and the elongation is measured. Letting the initial length be Lo, the length L when a load is applied between one regular piece is determined, and then the load is removed and left for another 10 minutes. The length at this time is L2 (
), then calculate the elongation recovery rate by elongation recovery rate = 33 EX・〇o (%).

The compression rate and compression recovery rate are determined by sampling 1 q square pieces of 10 x 1 ratio from a leather-like material, stacking these 10 pieces, and placing a thin metal plate (5 pieces) of the same size on top of the 10 pieces. ,
Leave it for 2 minutes and its thickness t.

Then, a load of 10k9 was applied evenly over the entire surface and left for 30 minutes. The thickness t after 30 minutes under load is measured, then the load is removed and the thickness is left for another 30 minutes, and the thickness at that time is determined. From to, chi, t2, the compression rate and compression recovery rate are: Hoof rate = Kide xloo (%) Armpit recovery rate = Imohito XI.

It is given in 〇 (%).

Example 1 A cell using the copper ammonia method.

Pour the stock solution into water so that the weave of the single fiber is 0.15 denier from the 100-hole bush opening, and
Each 00 hole spinneret is assembled with a gathering guide when it is in a semi-solidified state, and the single fibers are self-adhered to each other in the longitudinal direction to form a 15-denier fiber, and then the whole is assembled to form a 15,000-denier toe. , scouring and drying. This tow was cut into 7 ribs with a cutter to make short fibers.

A dispersion liquid was prepared by gradually adding 600 grams of the obtained ultra-fine fiber East Stable having a length of 1 meter to 600 grams of the water while slowly waving it. Next, polyacrylamide (
A slurry liquid with a viscosity of 25 ps was prepared by adding 2 g of a 0.5% aqueous solution (manufactured by Meisei Ihi Gakusha), and the slurry was made into a slurry liquid with a basis weight of 100 yen/sheet using a hydroformer type oblique fourdrinier paper making machine. A short fiber paper sheet was obtained.

On the back side of this paper sheet, a coarse tricot line fabric (nylon 664M/milk f multifilament knitted fabric) with a basis weight of 50 mm is evenly spread and a two-layered sheet is formed as shown in Figure 5. And so.

Next, a high-pressure water jet was applied continuously from the paper-formed sheet side of this two-layered sheet to the entire surface from the 0.1 side diameter hole at a pressure of 20 k9/ground, and then the sheet was turned over. Then, a high-pressure water stream was applied in the same way from the striped side. Subsequently, the front and back sides of the sheet were treated with high-pressure water jets twice each at a pressure of 40 k9/base to entangle the short fibers and the striped fabric and make them unifyable. When the cross section of the sheet treated with high-pressure water was observed using a scanning electron microscope, no two-layer structure was observed, and the 19 fibers were divided into thin fibers and ultra-fine single fibers lengthwise. It shows a three-dimensional intertwined structure in which the material is segmented and intertwined with the knitted fabric, and the non-woven layer and the knitted fabric layer are intricately intertwined to form an intricate non-woven fiber structure sheet. It had a cross-sectional structure just like the one shown in Figure 1.

This non-woven fibrous structure has a ratio of 30:7 of fibrous material and monofilament.
It was an extremely dense sheet-like material with a mixed ratio of 0.

(Density 0.Madarayu/ground) The integrated fiber structure of fine fiber and knitted fabric obtained in this way is extremely flexible and has a smooth surface, making it an interesting material for clothing. It has a texture.

Non-woven fiber structure weight 1
48 evening/me thickness
0.45 side density 0. $Y/ground Tensile strength Length 86 x Work 8.2 (k9/K9) Tensile elongation at break 91 x 73 (%) Tear strength 3.8 x 4.1 (K9)
Sewing strength 〃51×〃6.2 (k9/en)
Flexibility: Length 32 x Width 36 (wind) Elongation recovery rate
〃95×〃93(%) Compression rate
27(%) compression recovery rate
94 (%) This nonwoven fiber structure was soaked with a 15% DMF solution of polyurethane elastomer and squeezed with a mangle at a squeezing rate of 300%.

Next, the polyurethane was gently placed into a 30% DMF aqueous solution and left for 30 minutes to fully solidify the polyurethane. After washing and drying, the surface was brushed with sandpaper, resulting in a nubuck-like artificial leather with an extremely fine grained surface. When the surface of this nubuck was observed under an optical microscope, it was found that the surface had downy fuzz, which was a mixture of fine fiber fuzz and ultrafine fiber fuzz, as shown in Figure 8A.

The physical properties of the nubuck-like artificial leather according to the present invention were as shown below.

Fabric weight: 163mm/metal thickness
0.3 wind fiber/polyurethane 77/23 (weight ratio) density
0.39 / Uniform tensile strength Vertical 8.8
× 穣83 (k9/en) tensile elongation at break 〃93
×〃75(%) Tear strength〃4.1×〃4
．． 2(k9) Sewing strength〃5.2×〃6.4(
k9/enemy) Flexibility 〃35×〃41(
Skin) Elongation recovery rate 〃97×〃95(%) Compression rate 36(%) Compression recovery rate
95 (%) Comparative Example A Sazo sheet (wet weight: 150 yen/rudder) obtained in the same manner as in Example 1 was treated with a high-pressure water jet without laying the 1-knit fabric on the back side.

The treatment conditions and procedures were exactly the same as those in Example 1, but when treated with a high-pressure water stream, the sheet was stretched in the lateral direction and spread out, resulting in a hard texture. It was bad. That is, although the fibers and the single fibers are slightly intertwined, compared to the nonwoven fiber structure of Example 1, it does not feel like a nonwoven fabric and has a paper-like feel. Furthermore, when viewed under an electron microscope, it appears that there are few fibers oriented vertically, making it less complete.

The physical properties of this thin and smooth nonwoven fabric are shown below. Metsukedo 1$ evening/me thickness
0.2 material density
0.46 m/ground tensile strength vertical 2.6×
Width 2.1 (kg/enemy) Tensile elongation at break 〃31
×〃42(%) Tear strength〃0.9×〃
1.2 (k9) Sewing strength 〃1.6×〃0.
8 ([9/enemy) flexibility length 66 x machine 7
8 (Field) Extension recovery rate〃37×〃20(%)
Compression rate: 7 (%) Compression recovery rate: 100 (%) Next, Example 1
When impregnated with the same urethane elastomer solution and squeezed with a mangle, the sheet did not recover to its original thickness.
It remains compressed.

Next, the physical properties of the leather-like product obtained by surface raising are shown below. The appearance of the fluff on the surface looks like it has been picked up by lying fibers.
There was a lot of fluff that was curled up.

Fabric weight: 146 mm/Pillow thickness: 0.23 fence fiber/
Polyurethane: 91/9 (weight ratio) density
0. Muscle strength/ground tensile strength Vertical 3.1
× Lateral 2.6 (k9/arc) Tensile elongation at break〃4
3×〃52(%) Tear strength ″0.9×
〃1.2 (k9) Sewing strength 〃1.4×〃1.
1 (k9/enemy) Flexibility 〃75×〃9
3 (Skin) Elongation recovery rate Height 52 x Wisteria 30 (%
) Compression rate 5% compression recovery rate
100% When these values are compared with the physical properties of the leather-like material of Example 1, it can be easily understood that the strength relationships such as tensile strength are extremely low, and the leather-like material lacks a sense of fulfillment.

In other words, it is noticeably less thick for the same amount of fabric,
Furthermore, the elasticity is poor with a compression rate of only 5%, and the flexibility is also extremely poor. This shows how important the presence of knitted fabrics is, and the presence of knitted fabrics promotes intertwining.
Furthermore, it has been shown that vertical fibers can be produced to provide a highly elastic nonwoven fibrous structure. Example 2 Sea-island fibers were made into fused paper yarn using 40 parts by weight of nylon 6 (relative sulfuric acid viscosity 7y = 3.2) as the island component and 60 parts by weight of polystyrene (Styron GP-679 manufactured by Asahi Dow Co., Ltd.) as the sea component. Obtained.

The sea component of this sea-island fiber is extracted with 5 picoC chloroform and the single yarn denier is 0. On the other hand, Fiber East denier 1 red ultra-fine Fiber East was obtained. Next, this ultra-fine fiber East is treated with 3 and 9/ground steam to lightly fuse the single fibers within the fiber East, and then crimped using a pressing machine and cut into 35 pieces to form staples. did.

This staple was made into a random weave using a card machine, and a cross-laid web with a basis weight of 120 mm was obtained using a cross-layer.

Next, on the back side of this crosslaid web, a woven fabric made of case-like polyester fibers of 3/24f and having a basis weight of 55/m/m was laminated to form a sheet with a two-layer laminated structure. This two-layer laminated sheet material was needle punched with a sub/i ratio h2 of 100, and then entangled and entangled with a high-pressure water stream of 40k9/fence twice on each side, resulting in the same results as shown in Figure 1. A fiber structure having a structure in which ultra-fine single fibers, fibers having various thicknesses of various sizes, and a woven fabric were integrated was obtained. The mixing ratio of the fibers and the single fibers constituting this fiber structure was 20:80, and the density was 0.37 m/m.

Furthermore, the nonwoven fiber structure was soft and elastic, and its physical properties showed the following values. basis weight
170 evenings/pillow thickness
0.46 rib density 0.
37 Yu / Ground tensile strength Length 7.5 x Fuji 6.3 (k
9/skin) Tensile elongation at break 〃62×〃81(%
) Tear strength〃3.9×〃4.1(k9
)Sewing strength〃4.8×〃3.7 (k9/skin)
Flexibility 〃34×〃Satoshi (side) Elongation recovery rate 〃89×〃92(%) Compression rate
25(%) compression recovery rate
91 (%) This nonwoven fiber structure was impregnated with polyurethane elastomer in the same manner as in Example 1, coagulated, and then surface raised, resulting in a nubuck-like artificial material with extremely fine downy fluff on the surface. I was able to get some leather. Similar to that obtained in Example 1, this leather-like material also has fluff of the entire ultra-fine single fibers between the fluffs of the thin fibers.

It was an artificial leather with a fluffy appearance as shown in Figure 8A. The physical properties of the bound artificial leather are shown below. basis weight
Pine 0 evening/pillow thickness
0.55 rib density 0.
41/Fiber/Polyurethane 75/25 (weight ratio)
Tensile strength Length 83 x machine 7.5 (k9/en) Tensile elongation at break 77 x 90 (%) Tear strength
〃4.2×〃4.8 (k9) Sewing strength
〃55×〃4.2 (kg/enemy) Flexibility
〃39×〃41 (rib) extension recovery rate
〃93×〃93(%) Compression rate
31(%) Compression recovery rate 93(
%) Comparative Example 2 The composite fiber with a sea-island cross-sectional structure obtained in Example 2 was used as it was without extracting the sea component, crimped, cut on the 35 side, and then processed using a carding machine and a cross layer. , I got that cross raid web with a basis weight of 300 yen.

Next, the same polyester fiber fabric as that used in Example 2 was placed on the back side, and needle punching and high pressure water jet treatment were performed under the same conditions to obtain a nonwoven fabric. This nonwoven fabric was a fibrous structure in which woven fabric and sea-island fibers were entangled.

When this non-woven material was treated with boiling point refluxed trichlene to extract styrene, which is the sea component of sea-island fibers, only fiber east was present, and only this fiber east was intertwined with the fabric. The density of this material was 0.19 m/m, which was an extremely coarse sheet material. The physical properties of this three-dimensional entangled body of textiles are shown below. basis weight
Pine 0 Yu/Pillow thickness 1.
1 Wind density 0.19/ground tensile strength Length 4.2 x Fuji 3.7 (k9/arc) Tensile breaking elongation Length 78 x Width 90 (%) Tear strength
〃2.2×〃2.6 ([9) Sewing strength
〃1.4×〃2.1 (k9/arc) Flexibility
〃32×〃34 (kite) extension recovery rate
72 x mottling (%) compression rate
42 (%) compression recovery rate 5
1 (%) As shown by these physical properties, it is a nonwoven fabric-like material that is not tight and has a poor compression recovery rate, and shows that the density cannot be increased sufficiently if the fibers are entangled only.

One of the reasons for this is thought to be that the fibers are in the form of thick monofilaments called sea-island fibers at the intertwining stage of forming the non-woven fabric. In the case of the present invention, ultrafine fibers in which single fibers are properly bonded to each other, that is, multifilaments, are used, so that the fibers are intertwined and at the same time split and further divided into single fibers, making the nonwoven fabric more delicate. It is something that can be made into something.

Next, when urethane was impregnated and coagulated and the surface was brushed, it had no elasticity when squeezed during the urethane impregnation, so the thickness did not recover and it became flat, and furthermore, the surface condition was rough and looked like a cheap product. It has become.

The nonwoven fabric layer of this leather-like material was composed of only the fibers intertwined as shown in FIG. 3, and showed a structure in which polyurethane coagulated in large lumps in the voids.

In addition, the fluff covering the surface was entirely composed of fibers, and it showed a raised state just like the opening in Figure 8, giving it a rough texture. The physical properties of the obtained leather-like material are shown below. Area weight: 28
5 Tano thickness 0.6 side density
0.47 Tano fiber/Polyurethane = 77/23 (weight ratio) Tensile strength Length 4.5 x Width 3.9 (K9/
(K9) Tensile elongation at break 82 x 97 (%) Tear strength 2.4 x 3.1 (k9) Sewing strength 1.5 x 2.1 (k9/skin) Flexibility
Length 62 x width 59 (rib) elongation recovery rate
〃76×〃Satoshi (%) compression rate
12(%) compression recovery rate
I (%) The difference between the leather-like material of Comparative Example 2 and the leather-like material of Example 2 is noticeable in a decrease in strength, a decrease in compressibility, and a decrease in flexibility. This shows that non-woven materials and leather-like materials that are three-dimensionally intertwined do not satisfy the object of the present invention.

Example 3 Polyacrylonitrile dissolved in concentrated nitric acid was extruded into a diluted nitric acid solution through a weave opening (60 holes) with a hole diameter of 0.1 rib, and coagulated into a fiber.

After thoroughly washing with water, it was stretched approximately 8 times in a steam box, and then allowed to remain in a 50% aqueous solution of DM, and then dried at 100 qo to form a self-adhesive 18 denier/60 filament (single fiber). Acrylic fibers with a roughness of 0.3 denier were obtained. This self-adhesive acrylic fiber was cut into 5 pieces to make short fibers.

800 grams of the obtained short fibers were added to a dispersion layer containing 1,200 grams of water while slowly stirring to prepare a dispersion. Next, a 0.5% aqueous solution of polyacrylamide was added to this dispersion for 3 nights to obtain a slurry liquid with a viscosity of 15 ps, which was then made into a paper using a hydroformer-type long-slanted silk paper-making machine to obtain a basis weight. 150 evenings/end paper sheet was obtained.

The back side of this paper sheet is a double-sided bran fabric (knitted fabric made of nylon 6.30 denier/24 filament multifilament fiber).

A two-layer structure with a basis weight of 40 mm/m) was applied as shown in Figure 5, and then high-pressure water jet processing was performed under the same conditions as in Example 1 to form a mixture of finely divided single fibers. A nonwoven fiber structure was obtained in which the uneven ridges were integrated with the knitted fabric. In general, this product had the structure shown in FIG. 1, the ratio of total single fibers to fiber bundles was 85/15, and it was an extremely soft and elastic fiber sheet-like product.

The integral synthetic fiber structure of ultrafine fibers and knitted fabric thus obtained was impregnated with a 12% solution of polyurethane elastomer in methyl ethyl ketone, and squeezed with a mangle at a squeezing rate of 300%.

Next, the polyurethane was placed in 3,500 ml of water and left for 30 minutes to fully coagulate the polyurethane. After washing and drying, the surface was brushed with sandpaper to obtain nubuck-like artificial leather with an extremely fine grained surface. When this nubuck-like surface was observed with an optical microscope, it was found that there was a raised state as shown in Figure 8A, consisting of some fuzz on the east side of the fibers and most of the fuzz on the entire single fibers. The physical properties of the nubuck-like artificial leather of the present invention are shown below. basis weight
236 evening/me thickness
・0.7 pig density 0
．． 34 Yu/Fiber/Urethane 80/20 (weight ratio) Tensile strength Length 7.9 x Blind 7.5 (K9/
Skin) Tensile elongation at break 〃93×〃105(%)
Tear strength 4.9 x 4.2 ([9) Sewing strength Length x 4.2 x Width 39 (k9/melon) Flexibility
〃36×〃31 (skin) elongation recovery rate
〃89×〃81(%) Compression rate
26(%) compression recovery rate
90 (%) Comparative Example 3 A sheet made of the acrylic ultrafine fiber Higashi obtained in Example 3 and having a basis weight of 150 was individually subjected to high-pressure water jet treatment to form a three-dimensional entangled sheet.

The basis weight of this sheet was 150 yen/me. The double-sided green space used in Example 3 was laid on the back side of this non-woven fabric, and the ION
A lightly bonded two-layer structure sheet was obtained by needle-punching the mixture/iMh2. This two-layer structure sheet has the structure shown in FIG. 2, and almost no fibers or single fibers penetrating or intermingling between the textures of the paper base were found. In this two-layer structure,
Urethane was impregnated in the same manner as in Example 3 to obtain a leather-like material.

The surface condition of this product was as follows compared to that of the leather-like material obtained in Example 3.
There was a lot of fluff lying on the side, and the hair was not in a state of elasticity.

However, the fluff was a mixture of single fibers and fibers. Regarding other physical properties, the product was significantly inferior in strength, compressibility, compression recovery rate, and flexibility, and was a leather-like product with no value compared to the product of the present invention. It is impossible to provide the characteristics of the product of the present invention with a simple two-layer structure, and it is clear that the fibers and single fibers have a three-dimensional intertwined structure in which the bran fabric and the bran fabric are integrated. It shows that it is important. The physical properties of the two-layered leather-like material obtained in Comparative Example 3 are as follows. basis weight
235 evening / Thickness 0
．． 5th side density 0.47/m fiber/polyurethane 80/20 tensile strength length 4
．． 7 x horizontal 3.9 (k9/en) tensile elongation at break
〃82×〃96(%) Tear strength 〃2.
1×〃1.7 (kg) Sewing strength〃1.2×〃
1.6 (k9/skin) Softness: Length 69×
Horizontal 63 (skin) elongation recovery rate 〃52×〃71
(%) Compression rate 8 (%) Compression recovery rate 62 (%)

[Brief explanation of the drawing]

FIG. 1 is a diagram schematically showing the cross-sectional structure and the state of fluff on the surface of the nonwoven fiber structure and leather-like article of the present invention. FIG. 2 is a diagram schematically showing a two-layer structure sheet product other than the present invention, in which there is a sheet having a nonwoven fabric structure in the upper part, and a wire fabric in the lower part exists without interference with the upper nonwoven fabric. FIG. 3 is a diagram schematically showing the cross-sectional structure and surface condition of a nonwoven fabric other than the present invention, which consists essentially only of fibers. FIG. 4 is a diagram schematically showing the cross-sectional structure of natural leather. FIG. 5 is a schematic diagram of an example of an intermediate used to obtain the product of the present invention. FIG. 6 is a diagram showing the shape of a sample and measurement conditions when measuring the tear strength of a sheet-like material.
FIG. 7 is a diagram showing the state of the sample and details of the sewn portion when measuring the sewing strength. FIG. 8A is a diagram schematically showing the state of fluff when the surface of the leather-like material of the present invention is raised. FIG. 8 is a diagram schematically showing the state of fluff when the surface of a leather-like material made only of fibers other than those of the present invention is raised. Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8

Claims (1)

[Scope of Claims] 1 A structure consisting of fiber bundles of various sizes and thicknesses, single fibers subdivided from the fiber bundles, and knitted fabrics, where the knitted fabrics are attached to the back side or back side of the structure. Exist in the area,
A non-woven fiber structure characterized by having a three-dimensional mutual entanglement in which fiber bundles and single fibers are mixed, and a random entanglement in which these fibers enter the structure of a knitted fabric, resulting in an inseparable and integral structure as a whole. 2. The nonwoven fiber structure according to claim 1, wherein the single fiber fineness is 0.5 denier or less. 3. The knitted fabric has a basis weight of 10 to 100 g/m^2, and is present on the back surface or surface area in a proportion not exceeding 70% by weight of the entire basis weight of the nonwoven fiber structure. A nonwoven fibrous structure according to claim 1. 4 The fiber length of the single fibers and single fibers constituting the fiber bundle is 10
2. The nonwoven fiber structure according to claim 1, wherein the nonwoven fiber structure has a diameter of 1 mm or less. 5. A structure consisting of a fiber bundle of various sizes and thickness made of fibers with a single fiber fineness of 0.5 denier or less, single fibers subdivided from this fiber bundle, and knitted fabrics,
The knitted fabric exists on the back side or back surface area of this structure, and the three-dimensional mutual entanglement of fiber bundles and single fibers, and the random entanglement of these into the structure of the knitted fabric, create an overall structure. A nonwoven fibrous structure characterized by having an inseparable and integral structure and having a rubber-like elastic polymer interposed in the interstitial spaces of the entire structure. 6 The fiber length of the single fibers and single fibers constituting the fiber bundle is 10
6. The nonwoven fibrous structure according to claim 5, wherein the nonwoven fiber structure has a diameter of less than mm. 7 The basis weight of the knitted fabric is 30 to 70 g/m^2,
The nonwoven fibrous structure according to claim 5, wherein the nonwoven fibrous structure is present on the back surface or the back surface region in a range of 40 to 10% by weight of the entire basis weight of the nonwoven fibrous structure. 8. The nonwoven fibrous structure according to claim 5, wherein the surface of the nonwoven fibrous structure is fluffed.