JP5098554B2 - Leather-like sheet manufacturing method - Google Patents

Description

  The present invention relates to a leather-like sheet mainly made of ultrafine fiber nonwoven fabric and having an appearance similar to leather such as suede and nubuck, and a method for producing the same.

  A leather-like sheet made of an ultra-fine fiber nonwoven fabric and an elastic resin has a touch similar to that of natural leather, and has an excellent characteristic that is not found in natural leather, such as easy care, and is widely used.

Along with the expansion of applications, a higher level of flexibility than ever is required, and various proposals have been made to satisfy this requirement.
In the production of the ultrafine fiber nonwoven fabric constituting the leather-like sheet, there is a method in which the filament spun from the spinneret is cut so that the fiber length becomes 3 to 100 mm, and a short fiber web is formed by a papermaking method or a card raid method. Has been adopted.

On the other hand, in the spunbond method, fibers spun from the spinneret are collected directly on a collection net to obtain a fiber web, which is much more efficient than the above-described method for producing a short fiber web. Good. In addition, since the nonwoven fabric made of the fiber web by the spunbond method has very few fiber cutting points compared to the nonwoven fabric made of the short fiber web, it has excellent physical properties such as tensile strength. Various applications to leather-like sheets have been studied.
For example, Patent Document 1 discloses a fiber nonwoven fabric made of ultrafine continuous filaments, which is produced by forming a fiber web with a composite fiber having a shape in which two or more kinds of polymers are bonded to each other, and dividing at a bonding portion by needle punching or fluid jet action. The method of obtaining is proposed.

  According to this method, an ultrafine fiber nonwoven fabric can be efficiently obtained, but since ultrafine fibers composed of two or more incompatible polymers are mixed, a conventional leather-like sheet in which the ultrafine fibers are composed of a single polymer. It was difficult to dye in a color like this. In addition, since the fibers are divided at the bonding portion to form ultrafine fibers, they are flexible compared to general fibers having a fiber diameter exceeding 1 dtex, but are not sufficient. In addition, in order to facilitate the division, since it has a cross section of a tuft shape of petals and tangerines, the fiber diameter is limited when the nap is formed, and the direction in which the fiber bends is limited, and sufficient color development cannot be obtained. It was difficult to obtain a lighting effect peculiar to leather-like sheets unless the size was reduced. In addition, it is considered effective to increase the degree of entanglement of the fibers in order to improve the wear resistance. However, in the method using a needle punch (hereinafter referred to as NP), if the treatment is strengthened, the fiber will be cut, so it is difficult to improve the physical properties. In the method using the fluid jet action, when the treatment is strengthened, the water flow rebounds on the surface of the nonwoven fabric, so that uniform treatment becomes difficult, and sufficient physical properties cannot be obtained by any means.

  As another means, a technique for leaving elongation by lowering the spinning speed and lowering the degree of orientation, at least one component of the composite fiber is a polymer that can be easily hydrolyzed, and the nonwoven fabric is subjected to alkali weight reduction processing, so that at least A technique for forming a void in a sheet by hydrolyzing and reducing the amount of one component is disclosed (see, for example, Patent Document 2).

  In these methods, the sheet is highly flexible because it is composed of fibers remaining in elongation and has voids, but because the degree of orientation of the fibers is low, the physical properties of the fibers are likely to be low. The form stability of the sheet tends to be low.

  As another softening technique, there is a technique that achieves flexibility by making it difficult for fibers to fall off by using a long-fiber nonwoven fabric through the NP and integrating the woven or knitted fabric, thereby reducing the amount of binder and fusion. (For example, refer patent document 3) Moreover, the technique which cut | disconnects a fiber while advancing the fiber arrangement | sequence to the thickness direction by NP process is also disclosed (for example, refer patent document 4).

  According to these technologies, there is an advantage that the flexibility of the sheet is improved by arranging the fibers in the thickness direction, and the potential distortion is removed by cutting the fibers so that wrinkles are not easily generated. However, in order to arrange the fibers sufficiently in the thickness direction by NP treatment, there is a high possibility that the fibers will be cut. If the fibers are cut, the physical properties which are the advantages of the long-fiber nonwoven fabric, and the weave as the reinforcing fabric There was a problem that the physical properties of the knitted fabric deteriorated.

  In order to prevent the fiber from being cut in the NP treatment, a technique for increasing the shrinkage in the NP process is disclosed (for example, see Patent Document 5).

  Moreover, there exists a manufacturing method including the process of carrying out hot water shrinkage | contraction after NP for the purpose of relaxation | moderation of a distortion (for example, refer patent document 6).

  According to these technologies, although certain effects can be obtained against deterioration of physical properties due to fiber cutting and wrinkles due to distortion, strength and form stability as a leather-like sheet even if NP is performed under the condition that fibers are not cut. It was difficult to achieve both a flexible texture.

Thus, a leather-like sheet having a soft texture and excellent appearance durability such as wear resistance has not been obtained.
JP-A-10-53948 JP 2004-84076 A JP-A 64-20368 JP 2000-273769 A JP 2006-2286 A JP 2006-2287 A

  The present invention provides a leather-like sheet excellent in the softness of the texture, the appearance when worn and the durability of weight loss, and a method for producing the same.

In order to solve the above problems, the present invention mainly has the following configuration. That is, in the method for producing a leather-like sheet of the present invention, a molten polymer is spun at a speed of 3000 to 6000 m / min, and the single fiber fineness is 1 to 50 dtex on a moving net under suction. following the step of collecting the composite fibers, comprising the following steps a, B, C and D, performs the B, C and D after the a, and performs the C to the B and simultaneously or later, superfine A method for producing a leather-like sheet, wherein the fibers are long fibers .
A A process of making the composite fiber into a nonwoven fabric by needle punching process B A process of converting the composite fiber into an ultrafine fiber having a single fiber fineness of 0.0001 to 0.5 dtex by an ultrafine fiber expression process. Process D The process of laminating and integrating the nonwoven fabric with a woven or knitted fabric having a twist number of constituent yarns of 200 T / m or more and a basis weight of 170 g / m ² or less.

  ADVANTAGE OF THE INVENTION According to this invention, the leather-like sheet | seat excellent in the softness of a texture and durability of an external appearance can be provided.

  The leather-like sheet | seat of this invention contains a very thin long fiber nonwoven fabric. The long fiber as used in the field of this invention means the fiber substantially continuous exceeding 100 mm. As will be described later, the leather-like sheet of the present invention has a portion that is cut because a part of the long fiber is cut to form napped. In this invention, the length of the ultrafine fiber extracted from the nonwoven fabric is measured directly, and the thing containing the fiber exceeding 100 mm is made into a long fiber nonwoven fabric. In addition, it is preferable that the ratio of continuous fibers exceeding 100 mm is high from the viewpoint that it is easy to obtain high physical properties due to continuous fibers, which is an advantage of long fibers.

  This ultrafine long fiber nonwoven fabric is made of ultrafine fibers having a single fiber fineness of 0.0001 to 0.5 dtex. The single fiber fineness of the ultrafine fiber is preferably 0.001 tex or more, and more preferably 0.005 dtex or more. Moreover, 0.3 dtex or less is preferable and 0.15 dtex or less is more preferable. If it is less than 0.0001 dtex, the strength decreases, which is not preferable. On the other hand, if it exceeds 0.5 dtex, the texture becomes stiff and it is difficult to obtain sufficient entanglement, which causes problems such as deterioration of surface quality and wear properties in the present invention, which is not preferable. Moreover, the fiber of the fineness exceeding said range may be contained in the range which does not impair the effect of this invention.

  The cross-sectional shape of the ultrafine fiber of the present invention is not particularly limited, but the ratio R / r of the minimum circumscribed circle diameter R and the maximum inscribed circle diameter r in the cross section is 1 to 1.4. Preferably, 1-1.3 are more preferable. When R / r in the cross section exceeds 1.4, it is difficult to obtain a lighting effect peculiar to a leather-like sheet in a flat cross-sectional shape because the direction in which the fiber bends is limited. It tends to be difficult to obtain color developability. The R / r in the cross section referred to in the present invention means a value obtained by dividing the diameter of the minimum circumscribed circle measured by observing the fiber cross section with a microscope or the like by the diameter of the maximum inscribed circle similarly observed.

  The polymer constituting the ultrafine fiber is not particularly limited as long as it is an inelastic polymer. The inelastic polymer referred to in the present invention means a polymer excluding fibers excellent in rubber-like elasticity such as polyether ester fibers and polyurethane fibers such as so-called spandex. By being made of a substantially non-elastic polymer fiber material, it is possible to achieve a rich texture without rubber feeling, and various effects such as easy recyclability, high color development, high light resistance, yellowing resistance, etc. This is because it can be achieved. As the inelastic polymer, for example, polyester, polyamide, polyolefin and the like can be used depending on the intended use, but polyester is preferable in terms of dyeability, strength, durability, and fastness. The polyester that can be preferably used in the present invention is a polymer synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, and can be used as long as it can be used as a composite fiber. It is not limited. Specifically, for example, polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polyethylene-1,2-bis (2- Chlorophenoxy) ethane-4,4′-dicarboxylate and the like. In the present invention, the most commonly used polyethylene terephthalate or a polyester copolymer mainly containing ethylene terephthalate units is preferably used.

  In the ultrafine long fiber nonwoven fabric in the present invention, the ultrafine fibers need to be entangled with each other. This is because the conventional entanglement that leaves the ultrafine fiber bundle cannot achieve the intended wear resistance property of the present invention. The state in which the ultrafine fibers are entangled with each other in the present invention refers to a state in which the ultrafine fibers are entangled to such an extent that the entanglement between the ultrafine fiber bundles is hardly observed.

Microfine long-fiber nonwoven fabric in the present invention is preferably the basis weight is that 30 g / ^{m 2} or more, more preferably 40 g / ^{m 2} or more, 50 g / ^{m 2} or more is more preferable. Also, the basis weight is preferably not more than 550 g / ^{m 2,} more preferably 350 g / ^{m 2} or less, more preferably 150 g / ^{m 2} or less. When the basis weight is less than 30 g / m ² , the appearance of the woven fabric and / or the knitted fabric is easily seen on the surface, and the quality is lowered, which is not preferable. Further, when the basis weight exceeds 550 g / m ² , the wear resistance property in the present invention tends to decrease, which is not preferable.

  The basis weight is measured in accordance with JIS L1096 8.4.2 (1999). If the basis weight of the ultra-thin fiber nonwoven fabric cannot be measured directly, the value measured for the basis weight of the leather-like sheet and the weave taken out from the leather-like sheet You may obtain | require the difference of the fabric weight of a knitted fabric.

  The leather-like sheet in the present invention is obtained by integrating the above-mentioned ultrafine fiber nonwoven fabric and the woven or knitted fabric, and at least a part of the ultrafine fiber needs to penetrate the woven or knitted fabric. This is because, by passing through the woven or knitted fabric, it is possible to prevent peeling of the ultra-thin long fiber nonwoven fabric and the woven or knitted fabric.

  In the present invention, at least a part of the ultrafine fiber penetrates the woven or knitted fabric. When the cross section obtained by cutting the sheet in the thickness direction is observed visually or under a microscope, the ultrafine fiber penetrates the woven or knitted fabric. It means that there are fibers, that is, ultrafine fibers reaching from one surface of the woven or knitted fabric to the other surface.

  Moreover, in the leather-like sheet | seat in this invention, it is preferable that there are few cut | disconnected things among the fibers which comprise a woven / knitted fabric. The fibers that make up the woven or knitted fabric are not cut, so that the physical properties of the woven or knitted fabric, such as tensile strength and tear strength, are not impaired, and the ultrafine fibers that penetrate the woven or knitted fabric and the fibers that make up the woven or knitted fabric are entangled. This is because the movement of the fibers can be suppressed and the wear resistance can be improved. When the front and back surfaces of the leather-like sheet are visually or microscopically observed in a range of at least 10 cm square, it is preferable that there are not five or more fiber cut ends of the fibers constituting the woven or knitted fabric.

  The woven or knitted fabric in the present invention is not particularly limited, and can be appropriately selected according to the target texture and function. For example, when high drape and stretch properties are imparted, the effect can be expressed on the leather-like sheet by using a woven or knitted fabric having high drape and stretch properties.

  The raw material of the woven or knitted fabric is not particularly limited. For example, natural fibers such as cotton, hemp, and wool, semi-synthetic fibers such as cellulose fibers, and synthetic fibers are used. Either short fibers or long fibers are appropriately selected. it can. A plurality of types of fibers may be used, for example, a blended yarn, a blended yarn, a long / short composite yarn, and may be woven or knitted.

  For example, polyester fiber or polyamide fiber can be used as the synthetic fiber, but a woven fabric composed of a composite fiber in which two or more kinds of polyester polymers are joined in a side-by-side type or an eccentric core-sheath type is used. Is preferable because it can impart excellent stretch properties and drape properties to the leather-like sheet.

  In addition, it is also a preferable aspect that the composite fiber joined to the woven fabric in the side-by-side type or the eccentric core-sheath type is used for either the warp yarn or the weft yarn, and the normal fiber is used for the other.

  The structure of the woven fabric is not particularly limited. For example, a single structure such as plain weave, satin weave, or oblique weave, double structure such as ventilated weave, pile structure such as velvet or velvet, entangled structure such as cocoon, crest weave, and weaving Either is acceptable.

  The structure of the knitted fabric is not particularly limited, and for example, a horizontal knitting such as a flat knitting, a rubber knitting, a double-sided knitting, and a lace knitting, and a vertical knitting such as denby, atlas, and cord can be appropriately selected.

  The single fiber fineness of the fibers constituting such a woven or knitted fabric is not particularly limited, but is preferably 1 dtex or more, and more preferably 2 dtex or more. Moreover, 15 dtex or less is preferable and 10 dtex or less is more preferable. This is because if it is less than 1 dtex, it is difficult to obtain the effect of imparting sufficient shape stability to the leather-like sheet, and if it exceeds 15 dtex, it is difficult to obtain flexibility.

In the present invention, the basis weight of the woven or knitted fabric is not particularly limited, but is preferably 20 g / m ² or more, and more preferably 40 g / m ² or more. Moreover, 170 g / m < ² > or less is preferable and 150 g / m < ² > or less is more preferable. If it is less than 20 g / m ² , the homogeneity due to misalignment tends to decrease, and the effect of imparting sufficient form stability to the leather-like sheet is difficult to obtain. On the other hand, when it exceeds 170 g / m ² , it is difficult to obtain flexibility. The basis weight in the present invention refers to a value measured according to JIS L1096 8.4.2 (1999).

  Furthermore, the weight ratio of the woven or knitted fabric to the leather-like sheet is preferably 20% or more, and more preferably 30% or more. Moreover, 80% or less is preferable and 70% or less is more preferable. If the weight ratio is less than 20%, it will be difficult to fully exhibit the functions of the woven or knitted fabric such as form stability, drape, and stretchability. If the weight ratio exceeds 80%, the influence of the woven or knitted fabric will be large, This is because it becomes difficult to obtain a rich texture of the ultrafine fiber nonwoven fabric. The weight ratio of the woven or knitted fabric of the present invention to the leather-like sheet refers to a value obtained by dividing the weight of only the woven or knitted fabric by the weight of the leather-like sheet.

Leather-like sheet of the present invention is preferably the basis weight is that 80 g / ^{m 2} or more, more preferably 100 g / ^{m 2} or more, 120 g / ^{m 2} or more is more preferable. Further, it is preferably 650 g / ^{m 2} or less, more preferably 500 g / ^{m 2} or less, 350 g / ^{m 2} or less is more preferred. When the basis weight is less than 80 g / m ^2, it is difficult to obtain form stability against tension or tearing, and when it exceeds 650 g / m ² , it is difficult to obtain sufficient flexibility, which is not preferable.

Further, the apparent density of the leather-like sheet of the present invention is preferably not 0.200 g / cm ³ or more, more preferably 0.210 g / cm ³ or more, and particularly preferably 0.220 g / cm ³ or more. Also, preferably at 0.500 g / cm ³ or less, more preferably 0.400 g / cm ³ or less, particularly preferably 0.350 g / cm ³ or less. When the apparent density is less than 0.200 g / cm ³ , it becomes difficult to obtain sufficient strength and wear resistance in the present invention, such as tearing and stroking when dyeing is performed. On the other hand, if the apparent density exceeds 0.500 g / cm ³ , it becomes difficult to obtain the intended flexibility of the present invention, which is not preferable.

  The basis weight is measured according to JIS L1096 8.4.2 (1999), and the apparent density is measured according to JIS L1096 8.4.2 (1999), and then the thickness thereof is measured to obtain the apparent density. The average density was taken as the apparent density. For thickness measurement, a dial thickness gauge (trade name; Peacock H, manufactured by Ozaki Seisakusho Co., Ltd.) was used, and 10 arbitrary positions of the sample were measured, and the average value was used. The apparent density in the present invention refers to the apparent density of the fiber material.

  In addition, the leather-like sheet of the present invention preferably has a tensile strength in the vertical and horizontal directions of 70 N / cm or more. When the tensile strength in either the vertical or horizontal direction is less than 70 N / cm, when a leather-like sheet is used, process passability in the next higher-order processing step is deteriorated, and there is a tendency that tearing, dimensional change, etc. occur. Therefore, it is not preferable. Further, when a leather-like sheet is used, it is necessary to add a large amount of binder in order to obtain sufficient physical properties, and there is a problem that the texture tends to be hard. In addition, although the upper limit of this tensile strength is not specifically limited, Usually, it will be 200 N / cm or less. Here, the tensile strength was measured according to JIS L 1096 8.12.1 (1999), a sample having a width of 5 cm and a length of 20 cm, and a tensile speed of 10 cm / min with a constant-speed extension type tensile tester at a gripping interval of 10 cm. It was obtained by elongating. From the obtained value, the load per 1 cm width was defined as tensile strength (unit: N / cm). In order to obtain these strengths, the strength of the fibers used is preferably 2 cN / dtex or more.

  Furthermore, the leather-like sheet in the present invention preferably has a tear strength in the vertical and horizontal directions of 5 to 30N. When the tearing strength in either the vertical or horizontal direction is less than 3N, the process passability is lowered and stable production becomes difficult. On the other hand, if the tearing strength in either the vertical or horizontal direction exceeds 50 N, it generally tends to be too soft and it is difficult to balance with the texture. The tear strength was measured based on JIS L 1096 8.15.1 (1999) D method (pendulum method).

  These tear strengths can be achieved by adjusting the apparent density to an appropriate range, and generally the strength tends to decrease as the density increases.

  In the leather-like sheet of the present invention, the stress at 10% elongation in the vertical direction is preferably 8 N / cm or more in order to prevent the sheet from being deformed or torn in a subsequent process depending on the application. It is more preferable that The upper limit of the stress at the time of 10% elongation is not particularly limited, but if it exceeds 50 N / cm, the texture is hardened and workability is lowered, which is not preferable. In the case of manufacturing by the above-described manufacturing method, the stress value at the time of 10% elongation can be improved by sufficiently performing NP processing or high-speed fluid processing. Moreover, the value of such stress can be increased by laminating woven fabric and / or knitted fabric.

  The stress (modulus) at 10% elongation was measured in the same manner as the tensile strength measurement method, and the strength at 10% elongation was taken as the value.

  The physical properties of the leather-like sheet described above are important elements for obtaining the wear-resistant physical properties in the present invention, and this can be achieved by entanglement of ultrafine fibers as will be described later.

  Furthermore, the leather-like sheet of the present invention has an appearance of grade 3 or higher and a weight loss of 10 mg or less in the abrasion resistance evaluation.

  The abrasion resistance evaluation referred to in the present invention is 3,000 times and 20000 times in an abrasion resistance test measured according to JIS L 1096 (1999) 8.17.5 E method (Martindale method) furniture load (12 kPa). The appearance of the test cloth after the number of times of wear is determined by the judgment standard table of JIS L 1076 (1999) Table 2. In the present invention, it is necessary to have grades 3 to 5 for both 3000 times and 20000 times. If it is less than the third grade, sufficient quality cannot be maintained, and the fifth grade is the most preferable state for evaluation. Conventionally, napped leather-like sheets have been evaluated by the number of times until the fabric layer is exposed as described in Japanese Patent Application Laid-Open No. 2003-268680 as an end point on appearance. However, in the case where dings and pills are generated even when the fabric layer is not exposed, there is a problem that the number of times until the fabric layer is exposed does not necessarily match the durability of the surface. Therefore, the wear resistance evaluation of the present invention is based on the judgment standard table of JIS L 1076 (1999) Table 2, and the appearance change such as the presence or absence of pills is assumed 3000 times after short-term use and after long-term use. It is evaluated at 20000 times. In particular, it is important to show the stability of the form that the appearance does not change significantly after 20000 times, but the appearance change may be large in short-term use. Therefore, in the present invention, a higher level of durability can be achieved by no change even after 3000 times. Furthermore, in a wear resistance test measured according to JIS L 1096 (1999) 8.17.5 E method (Martindale method) furniture load (12 kPa), the weight loss after 20000 times is 10 mg or less. The wear loss is more preferably 5 mg or less. When wear loss exceeds 10 mg, fluff tends to adhere to clothes and the like in actual use, which is not preferable. On the other hand, the lower limit is not particularly limited, and the napped leather-like sheet of the present invention can be obtained with almost no wear loss.

  The leather-like sheet of the present invention preferably has a bending resistance of 0.1 to 1.0 mN. When the bending resistance is less than 0.1 mN, the form stability tends to be insufficient, and the texture tends to be unsatisfactory. On the other hand, if the bending resistance exceeds 1.0 mN, the flexibility becomes insufficient, which is not preferable. The bending resistance in the present invention is a value measured at a length of 38 mm and a width of 25 mm in a bending resilience test measured according to JIS L 1096 (1999) 8.20.1 A method (Gurley method). is there. These bending resistances can be achieved by adjusting the bending resistance, basis weight, and apparent density of the woven or knitted fabric to appropriate ranges.

The leather-like sheet of the present invention is substantially free of a polymer elastic body such as polyurethane and is substantially made of a fiber material of an inelastic polymer.
The term “substantially composed of a non-elastic polymer fiber material” as used herein means that the content of the binder composed of a polymer elastic body such as polyurethane is less than 5% by weight, preferably the binder Less than 3% by weight on the fiber, more preferably less than 1% by weight on the fiber, most preferably no binder.

  The fiber of the non-elastic polymer here means a polymer excluding a fiber excellent in rubber-like elasticity such as a polyether-based fiber or a polyurethane-based fiber such as so-called spandex as described above, and particularly for performing chemical recycling. The fiber material is preferably made of polyethylene terephthalate or nylon 6. The leather-like sheet of the present invention is most preferably one that does not contain any polymer elastic body such as polyether-based fibers or polyurethane fibers such as spandex. However, it does not deviate from the effects of the present invention. It does not matter if the body is included. In addition, functional agents such as dyes, softeners, texture modifiers, pilling inhibitors, antibacterial agents, deodorants, water repellents, light proofing agents, and antifungal agents may be included.

  The leather-like sheet of the present invention is a leather-like sheet made of a non-elastic polymer fiber material, which is composed of an extra-fine long-fiber nonwoven fabric and a woven or knitted fabric.

  The leather-like sheet here has a surface appearance excellent in suede, nubuck, silver surface, etc. like natural leather, and particularly preferred in the present invention is a napped appearance such as suede or nubuck. In, it has a smooth touch and excellent lighting effects.

In the leather-like sheet of the present invention, it is preferable that the fibers constituting the ultrafine long-fiber non-woven fabric form napped. The length of this napping is not particularly limited, and it can have various napping lengths like natural leather such as velor, suede and nubuck, but the napping length in terms of excellent wear resistance in the present invention. Those having a short nubuck-like appearance are preferred. Moreover, it is preferable to dye | stain an ultrafine long fiber nonwoven fabric.
Furthermore, a structure in which a woven or knitted fabric is sandwiched between non-woven fabrics that are the same as or different from the ultra-fine long-fiber non-woven fabric is also preferable in that the outer and outer surfaces of the woven or knitted fabric have an appearance of a non-woven fabric.

Next, a method for producing the leather-like sheet of the present invention will be described.
First, a method for producing the ultra-thin fiber nonwoven fabric in the present invention will be described.

  There is no particular limitation on the production method of so-called ultrafine fibers having a single fiber fineness in the range of 0.0001 to 0.5 dtex. For example, a method of directly spinning ultrafine fibers, a normal fineness fiber that generates ultrafine fibers. There is a method in which fibers (composite fibers) that can be formed are spun, and then ultrafine fibers are generated by ultrafine fiber expression treatment (ultrafine treatment).

  And, as a method of using a composite fiber, for example, it can be manufactured by means such as a method of removing sea components after spinning a sea-island type composite fiber, a method of spinning and splitting a split-type composite fiber, and making it ultrafine. it can. Among these, in the present invention, it is preferable that the ultrafine fiber can be obtained easily and stably, and is preferably produced by a sea-island type composite fiber or a split type composite fiber. It is more preferable to manufacture with an island-in-sea type composite fiber in that an ultrafine fiber composed of the same kind of polymer that can be dyed with the above dye can be easily obtained.

  The sea-island type composite fiber as used in the present invention refers to a fiber in which two or more components are combined and mixed at an arbitrary stage to obtain a fiber cross-section in a sea-island state, and the method for obtaining this fiber is not particularly limited, For example, (1) a method in which two or more components are blended and spun in a chip state, (2) a method in which two or more components are kneaded in advance to form a chip, and then spun, (3) two components in a molten state A method of mixing the above polymer in a spinning machine pack using a static mixer, etc. (4) Manufactured using a die described in Japanese Patent Publication No. 44-18369, Japanese Patent Laid-Open No. 54-116417, etc. Method, etc. In the present invention, any method can be used to satisfactorily produce, but the method (4) is preferably employed because the selection of the polymer is easy.

  In order to make the sea-island type composite fiber into a non-woven fabric, for example, the above-mentioned polymer is discharged from the die shown in the above method (4), and at a speed of 3000 to 6000 m / min by an air jet method or a roller method. After stretching, it can be obtained by collecting on a collecting surface such as a web conveyor. At this time, if the stretching and collection are continuously performed by the air jet method, it is not necessary to open the fiber after winding up, which is preferable in terms of productivity. Here, the air jet method is a method of drawing and spinning a spun yarn by air using an ejector or air soccer.

  In addition, when using split type composite fiber, it can mainly carry out according to the manufacturing method of the above-mentioned sea-island type composite fiber by compounding two or more components in the die.

  In the method of (4), the cross-sectional shape of the island fiber obtained by removing the sea-island type composite fiber and the sea component is not particularly limited, and for example, round, polygonal, Y, H, X, W, C, π type, etc. However, in the present invention, the ratio R / r of the diameter R of the minimum circumscribed circle and the diameter r of the maximum inscribed circle in the cross section is preferably in the range of 1 to 1.4 as described above. In order to achieve this range, the cross-sectional shape is preferably round.

  Further, the number of polymer species to be used is not particularly limited, but it is preferably 2 to 3 components in consideration of spinning stability and dyeability, and particularly composed of 2 components of sea 1 component and island 1 component. It is preferable. In addition, the component ratio at this time is preferably 0.30 or more, more preferably 0.40 or more, and further preferably 0.50 or more, by weight ratio of island fibers to sea-island composite fibers. Moreover, it is preferable that an upper limit is 0.99 or less by weight ratio, 0.97 or less is more preferable, and 0.80 or less is further more preferable. If it is less than 0.30, the removal rate of sea components increases, which is not preferable in terms of cost. On the other hand, when the ratio exceeds 0.99, the island components tend to be joined together, which is not preferable in terms of spinning stability.

  The polymer to be used is not particularly limited. For example, the island component is preferably polyester from the viewpoint of dyeability, strength, durability, and fastness as described above.

  The polymer used as the sea component of the sea-island composite fiber is not particularly limited as long as it has chemical properties that are higher in solubility and degradability than the polymer constituting the island component. Depending on the selection of the polymer constituting the island component, for example, polyolefins such as polyethylene and polystyrene, 5-sodium sulfoisophthalic acid, polyethylene glycol, sodium dodecylbenzenesulfonate, bisphenol A compound, isophthalic acid, adipic acid, dodecadioic acid, Polyester etc. which copolymerized cyclohexyl carboxylic acid etc. can be used. Polystyrene is preferable from the viewpoint of spinning stability, but a copolymer polyester having a sulfone group is preferable because it can be easily removed without using an organic solvent. The copolymerization ratio is preferably 5 mol% or more from the viewpoint of processing speed and stability, and 20 mol% or less from the viewpoint of ease of polymerization, spinning and stretching. A preferred combination in the present invention is a copolyester having polyester as the island component and polystyrene or sulfone group as the sea component.

  To these polymers, inorganic particles such as titanium oxide particles may be added to the polymer in order to improve the concealing property. In addition, lubricants, pigments, heat stabilizers, ultraviolet absorbers, conductive agents, heat storages, etc. An agent, an antibacterial agent and the like can be added according to various purposes.

  The single fiber fineness of the composite fiber thus obtained is in the range of 1 to 50 dtex. If the single fiber fineness is less than 1 dtex, it will be difficult to obtain a sufficient strength by cutting the fiber or needle barb by NP described later, and if it exceeds 50 dtex, the needle will be easily broken, which is not preferable.

  The single fiber fineness of the ultrafine fiber obtained from this composite fiber is 0.0001 dtex or more, preferably 0.001 dtex or more, and more preferably 0.005 dtex or more. Moreover, it is 0.5 dtex or less, 0.3 dtex or less is preferable and 0.15 dtex or less is more preferable. If it is less than 0.0001 dtex, the strength decreases, and if it exceeds 0.5 dtex, the texture becomes stiff, and sufficient entanglement is difficult to obtain in the high-speed fluid treatment described later, so that the surface quality and wear resistance in the present invention decrease. This is also undesirable. Moreover, the fiber of the fineness exceeding said range may be contained in the range which does not impair the effect of this invention.

  The method for setting the single fiber fineness of the ultrafine fiber in such a range is not particularly limited, and can be easily achieved by adjusting the supply amount of the island component polymer when manufacturing the above-described composite fiber.

  Next, a method for producing an ultrafine long fiber nonwoven fabric will be described.

In this invention, the following process is included following the process of collecting the composite fiber of 1-50 dtex mentioned above.
A A process of making the composite fiber into a nonwoven fabric by needle punching process B A process of converting the composite fiber into an ultrafine fiber having a single fiber fineness of 0.0001 to 0.5 dtex by an ultrafine fiber expression process. Step D The step of laminating and integrating the non-woven fabric with the woven or knitted fabric. That is, the non-woven fabric may be formed after obtaining the ultrafine fibers. A. After the composite fiber is made into a non-woven fabric by needle punching, In order to make ultrafine fiber non-woven fabric and make the ultrafine fiber entangled, C.I. This is a method for performing high-speed fluid treatment.

Nonwoven fabrics composed of such composite fibers include A. The step of NP treated composite fibers, fibers apparent density preferably in the 0.120 g / cm ³ or more, and more preferably set to 0.150 g / cm ³ or more. Further, preferably in the 0.300 g / cm ³ or less, and more preferably to 0.250 g / cm ³ or less. If it is less than 0.120 g / cm ³ , the entanglement is insufficient, and the desired physical properties are difficult to obtain. The upper limit is not particularly defined, but if it exceeds 0.300 g / cm ³ , problems such as fiber cutting, broken needle needles, and remaining needle holes are not preferred.

  In the NP treatment in the present invention, it is preferable that the fiber is sufficiently entangled together with the role of temporary fixing for obtaining process passability. However, since the wear resistance property of the present invention is obtained in the high-speed fluid treatment described later, the fiber It is preferable to perform NP treatment within a range that does not cut. In the conventional NP processing step, the D.D. When performing the process of laminating and integrating with the woven or knitted fabric, in addition to the above-described cutting of the non-woven fiber, there is a high possibility that the fibers constituting the woven or knitted fabric will also be cut. Since it is integrated, there is no such problem, and a leather-like sheet having both high physical properties and a flexible texture can be obtained.

The nonwoven fabric composed of the composite fiber thus obtained is preferably shrunk by dry heat and / or wet heat, and further densified.
After making a non-woven fabric made of a composite fiber using a composite fiber, By the ultrafine fiber expression treatment, the fine fiber is made ultrafine by a process of making ultrafine fibers having a single fiber fineness of 0.0001 to 0.5 dtex to obtain an ultrafine long fiber nonwoven fabric. A method for such ultrafine processing is not particularly limited, and examples thereof include a mechanical method and a chemical method. The mechanical method is a method of miniaturizing by applying a physical stimulus. For example, in addition to the method of applying an impact such as the NP method or the water jet punch (hereinafter referred to as WJP) method, the distance between rollers And a method of applying ultrasonic pressure, a method of performing ultrasonic treatment, and the like. The chemical method includes, for example, a method in which at least one component constituting the composite fiber is subjected to changes such as swelling, decomposition, and dissolution by a drug. In particular, the method of preparing a nonwoven fabric with a composite fiber comprising an alkali-degradable sea component and then treating it with a neutral to alkaline aqueous solution to make it ultrafine is preferable in terms of the working environment without using a solvent. This is one of the preferred embodiments. The neutral to alkaline aqueous solution here is an aqueous solution having a pH of 6 to 14, and the chemicals used are not particularly limited. For example, an aqueous solution containing organic or inorganic salts may be used as long as it exhibits a pH in the above range, and alkali metal salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate, calcium hydroxide, water Examples include alkaline earth metal salts such as magnesium oxide. Further, if necessary, amines such as triethanolamine, diethanolamine, monoethanolamine, a weight loss accelerator, a carrier, and the like can be used in combination. Of these, sodium hydroxide is preferable in terms of price and ease of handling. Furthermore, it is preferable that the sheet is subjected to the neutral to alkaline aqueous solution treatment described above, and then neutralized and washed as necessary to remove the remaining chemicals and decomposition products, and then dried.

  As described above, after obtaining the composite long fiber nonwoven fabric by the A process, the ultrafine fiber nonwoven fabric is obtained by ultrafinening by the B process. It is preferable to perform a high-speed fluid treatment step, for example, a WJP treatment using a water stream. By combining this NP treatment and high-speed fluid treatment, it is possible to highly entangle ultrafine fibers. The leather-like sheet-like material in the present invention can be obtained particularly by the above-described process because of the difference between the fiber that is easily entangled by NP and the fiber that is easily entangled by high-speed fluid treatment. In other words, the entanglement by NP is excellent when the fiber of 1 to 50 dtex is thick, and the entanglement by high-speed fluid treatment tends to be excellent in the ultrafine region of 0.0001 to 0.5 dtex. In order to combine these fiber fineness and the entanglement method, it is sufficiently entangled with NP using a composite fiber having a fineness of 1 to 50 dtex, and then subjected to ultrafine processing to obtain an ultrafine fiber of 0.0001 to 0.5 dtex, followed by high speed The method of performing fluid treatment is the most preferable production method. At this time, the knitted and knitted fabrics are laminated and subjected to high-speed fluid treatment to form an ultrafine long-fiber nonwoven fabric. It is preferable to perform a step of laminating and integrating the woven or knitted fabric. When the ultra-thin fiber non-woven fabric is subjected to high-speed fluid treatment and the basis weight of the ultra-thin fiber non-woven fabric is high, the reflection of the fluid increases and uniform treatment becomes difficult. For this reason, it has been difficult to obtain a high-weight nonwoven fabric imparted with a high degree of confounding by high-speed fluid treatment.

  Therefore, in the present invention, by laminating the woven or knitted fabric, a leather-like sheet having a high basis weight can be obtained even if the basis weight of the nonwoven fabric is small, and the load in the NP treatment can be reduced as compared with the method of laminating in the NP process. For this reason, it has been found that the problem of deterioration in physical properties due to cutting of the nonwoven composite fiber and the woven / knitted fiber is less likely to occur. In particular, in terms of tensile strength, tear strength, and abrasion resistance, it is preferable that the fibers constituting the woven or knitted fabric are not cut, but by laminating and integrating the woven and knitted fabric with the ultra-thin fiber nonwoven fabric by high-speed fluid treatment, A leather-like sheet can be obtained without cutting the fibers constituting the woven or knitted fabric.

  Furthermore, by integrating the obtained ultra-fine long fiber nonwoven fabric and the woven or knitted fabric, functions such as a target texture can be imparted by the woven or knitted fabric. For example, when high drape and stretch properties are imparted, the effect can be expressed in the leather-like sheet by integrating with a woven or knitted fabric having high drape and stretch properties.

  The manufacturing method of such a knitted or knitted fabric is not particularly limited, and a loom suitable for the required structure can be used. Examples of the loom include an air jet loom, a water jet loom, and a fly shuttle loom. At this time, if the weaving density is lowered too much, the reinforcing effect by the woven fabric is reduced, and if the weaving density is raised too much, the reflection of the fluid at the time of high-speed fluid treatment increases and it cannot be stably processed. It is preferable that the space is appropriately spaced.

  On the other hand, the manufacturing method of the knitted fabric is not particularly limited, and a knitting machine suitable for the required organization can be used. Examples of the knitting machine include a flat knitting machine, a circular knitting machine, a tricot machine, and a Russell machine.

  As a method for integrating the woven or knitted fabric and the ultra-thin fiber non-woven fabric obtained by these methods, various methods other than the entanglement method using the means such as NP treatment and high-speed fluid flow treatment, the adhesion method, and the like can be used. Or it is known to employ in combination. In the present invention, among these, the method by entanglement is adopted in that it is excellent in drapability, and high-speed fluid flow treatment is used in that it can be entangled without damaging the knit.

The constituent yarns constituting these woven or knitted fabrics preferably have a twist number of 100 T / m or more, and more preferably 200 T / m or more. Moreover, it is preferable to set it as 2000 T / m or less, and 1800 T / m or less is more preferable. If it is less than 100 T / m, the water permeability of the knitted or knitted fabric is low, and it is difficult to increase the flow rate due to reflection of the fluid when performing high-speed fluid treatment, and it is difficult to increase the flow rate, and if it exceeds 2000 T / m, the texture tends to become hard. It is. The number of twists referred to in the present invention is determined by the yarn length after untwisting the untwisted number when untwisted under a load of 90 × 10 ⁻³ cN / dtex by a tester and completely untwisted. It is the value.

  When high-speed fluid treatment is used to integrate the ultra-thin fiber nonwoven fabric and the woven or knitted fabric, the high-speed fluid treatment in the C process for the integration in the D process also serves as the ultra-thinning treatment of the composite long-fiber nonwoven fabric in the B process. It is also possible to make it. That is, the ultrafine fiber expression process and the high-speed fluid process for obtaining the entanglement are simultaneously performed. The process can be simplified by making the split fiber type composite fiber fine and entangled by high-speed fluid treatment, or by eluting and confounding components soluble in the high-speed fluid. However, it is preferable to perform high-speed fluid treatment even after at least most of the ultrafine processing has been completed in order to further entangle the ultrafine fibers, and it is preferable to perform high-speed fluid treatment after performing the ultrafine processing. .

  As the high-speed fluid processing, it is preferable to perform WJP processing using a water flow in terms of the working environment. At this time, it is preferable to perform the water in a columnar flow state. In order to obtain a columnar flow, it is usually obtained by ejecting from a hole having a hole diameter (diameter) of 0.06 to 1.0 mm at a pressure of 1 to 60 MPa. In order to obtain efficient entanglement and good surface quality, this treatment preferably has a hole diameter of 0.06 to 0.20 mm and a hole interval of 5 mm or less, a hole diameter of 0.06 to 0.15 mm, and a hole interval. Is more preferably 1 mm or less. When these hole specifications are processed a plurality of times, it is not necessary to make them all the same. For example, a nozzle having a large hole diameter and a small hole diameter can be used in combination, but the nozzle having the above configuration is used at least once. It is preferable. In particular, when the pore diameter exceeds 0.20 mm, a water flow hitting trace is strongly imparted to the surface, and the smoothness is lowered, which is not preferable. Further, if the hole diameter is less than 0.06 mm, clogging of holes is likely to occur, and this is not preferable because there is a problem that costs increase due to the necessity of highly filtering water.

  Moreover, the jetted water turns to the nonwoven fabric and rebounds on the upper surface of the nonwoven fabric and is removed through the suction box. At this time, the water splashing on the upper surface of the nonwoven fabric adversely affects the uniformity of the treatment, but by laminating the woven or knitted fabric as described above, it is possible to improve the water permeability and increase the proportion of water removed through the suction box. I found it. Therefore, by laminating the knitted or knitted fabric, it can be processed under conditions stronger than before, and the target wear resistance can be obtained.

  Further, for the purpose of achieving uniform entanglement in the thickness direction and / or improving the smoothness of the nonwoven fabric surface, the treatment is preferably repeated a number of times. Further, the water flow pressure is appropriately selected according to the basis weight of the nonwoven fabric to be treated, and the higher the basis weight, the higher the pressure. The term “multiple times” as used herein means that the number of passes through one nozzle plate having holes arranged in a direction orthogonal to the conveyer and / or cylinder to be conveyed is multiple times.

  In addition, you may perform a fluid immersion process before performing a high-speed fluid process to a composite long fiber nonwoven fabric or an ultrafine fiber nonwoven fabric. In order to further improve the surface quality, the nozzle head and the conveyor and / or cylinder transporting nonwoven fabric are moved in a different direction from the direction of travel of the cylinder, or a wire mesh or the like is inserted between the nonwoven fabric and the nozzle after entanglement. It is also possible to perform a method such as watering. In this way, the ultrafine fibers are preferably entangled until the vertical 10% modulus is 8 N / cm or more, more preferably 10 N / cm or more.

  In general, in the case of an ultrafine fiber obtained from a composite fiber, an ultrafine fiber bundle in which the fibers are converged is mainly entangled. An ultrafine fiber nonwoven fabric in which ultrafine fibers are highly entangled to such an extent that entanglement is hardly observed can be obtained, and the surface characteristics such as wear properties in the present invention can also be improved thereby.

  Moreover, since lamination | stacking of a woven / knitted fabric and an ultrafine long fiber nonwoven fabric can be achieved by entanglement integration by high-speed fluid processing, it is preferable to perform the said process of C and D simultaneously in this invention. As a result, high-speed fluid processing for the purpose of entanglement between ultrafine fibers and lamination and integration of woven and knitted fabrics can be performed simultaneously, so that the process can be simplified and the fibers are not cut unlike lamination integration by NP. High physical properties can be obtained. At this time, at least a part of the ultrafine fibers needs to penetrate the woven or knitted fabric. Penetration of woven or knitted fabric can be achieved by increasing the movement of fibers during high-speed fluid processing, so that the entanglement at NP is adjusted so as not to become extremely strong, the nozzle hole diameter used for high-speed fluid processing is increased, and high-speed fluid It can be obtained by such means as increasing the processing pressure and decreasing the processing speed of the high-speed fluid processing.

  Furthermore, a structure in which a woven or knitted fabric is sandwiched between non-woven fabrics that are the same as or different from the ultra-fine long-fiber non-woven fabric is also preferable in that the outer and outer surfaces of the woven or knitted fabric have an appearance of a non-woven fabric. The means for obtaining such a structure is not particularly limited. For example, water having an average fiber length of 0.1 to 1 cm and an average single fiber fineness of 0.01 to 0.5 decitex in water containing a water-soluble resin or the like. The short fiber nonwoven fabric and the woven or knitted fabric produced by refining and dispersing the dispersion liquid at a concentration of about 0.0001 to 0.1% by weight on a wire mesh are entangled with the woven or knitted fabric in advance by high-speed fluid treatment. The leather-like sheet comprising the ultrafine fiber nonwoven fabric, the woven fabric and the short fiber nonwoven fabric is obtained by overlapping the woven or knitted fabric side so as to be in contact with the ultrafine long fiber nonwoven fabric and further performing high-speed fluid treatment.

  Moreover, as a leather-like sheet | seat of this invention, it is preferable that at least one surface is raised. The leather-like sheet of the present invention is substantially made of a fiber material, but has a surface quality similar to that of general natural leather or artificial leather, unlike a simple nonwoven fabric. In addition, as described above, it is preferable that the napped length is short in terms of wear physical properties in the present invention. As a means for obtaining napping, it is preferable to perform napping treatment with sandpaper or a brush. Such brushing treatment can be performed before or after dyeing or before and after dyeing.

  And it is preferable that such a leather-like sheet is dyed. The method for dyeing this ultrafine short fiber nonwoven fabric is not particularly limited, and the dyeing machine used may be any of a liquid dyeing machine, a thermosol dyeing machine, a high-pressure jigger dyeing machine, etc. It is preferable to dye using a liquid dyeing machine in terms of excellent texture.

In the napped leather-like sheet of the present invention, fine particles can be imparted for the purpose of further improving the wear resistance in the present invention.
In the case of providing fine particles, the material of the fine particles is not particularly limited as long as it is insoluble in water, and examples include inorganic substances such as silica, colloidal silica, titanium oxide, aluminum, mica, and organic substances such as melamine resin. can do.

  The average particle diameter of the fine particles is preferably 0.001 μm or more, more preferably 0.01 μm or more, and even more preferably 0.05 μm or more, in that the washing durability is excellent and the effect of improving wear resistance is obtained. . Moreover, it is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. The average particle diameter of the fine particles can be measured using a measurement method suitable for each material and size, for example, a BET method, a laser method, a dynamic scattering method, a Coulter method, or the like. In the present invention, the volume (mass) average particle diameter determined using the BET method is particularly preferable.

  The content of these fine particles is preferably 0.01% by weight or more, more preferably 0.02% by weight or more of the leather-like sheet, in that the texture of the leather-like sheet does not become hard and an effect of improving wear resistance is obtained. Preferably, 0.05 weight% or more is more preferable. Moreover, 10 weight% or less is preferable, 5 weight% or less is more preferable, and 1 weight% or less is further more preferable.

As means for applying the fine particles, a pad method, a method using a liquid dyeing machine or a jigger dyeing machine, a spraying method, etc. can be selected as appropriate.
In addition, a texture modifier and an anti-pill agent are added as appropriate. As a means for applying a texture adjusting agent or an anti-pill agent, a pad method, a method using a liquid flow dyeing machine or a jigger dyeing machine, a spraying method, etc. can be appropriately selected.

  Moreover, in order to obtain a soft texture and a smooth surface touch, the leather-like sheet of the present invention preferably contains a softening agent. As the softening agent, it is preferable to appropriately select one generally used for woven or knitted fabrics according to the fiber type. For example, in the 23rd edition of Dyeing Note (Issue Color Co., Ltd., issued on August 31, 2002), those described under the names of texture finish and soft finish can be appropriately selected. Among these, a silicone emulsion is preferable in terms of excellent flexibility effect, and an amino-modified or epoxy-modified silicone emulsion is more preferable. When these softeners are included, the wear resistance tends to decrease. Therefore, the amount of the softener and the amount of the fine particles should be adjusted as appropriate while balancing the target texture and the wear resistance. Is preferred. Therefore, the amount is not particularly limited, but is preferably in the range of 0.01 to 10% by weight of the leather-like sheet in terms of balance between texture and wear resistance and suppression of stickiness.

  As a means for applying a softening agent to the leather-like sheet, a pad method, a method using a liquid dyeing machine or a jigger dyeing machine, a method of spraying with a spray, and the like can be appropriately selected as in the case of applying fine particles. From the viewpoint of cost, it is preferable to apply the fine particles and the softening agent simultaneously. The fine particles and softening agent are preferably applied after dyeing. If applied before dyeing, the effect may be reduced due to omission during dyeing or uneven dyeing may occur, which is not preferable.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the physical-property value in an Example was measured by the method described below.

(1) Weight per unit area and fiber apparent density The basis weight was measured by the method of JIS L 1096 8.4.2 (1999). Further, the thickness was measured with a dial thickness gauge (manufactured by Ozaki Mfg. Co., Ltd., trade name “Peacock H”), and the apparent fiber density was calculated from the basis weight value.

(2) Abrasion resistance property JIS L 1096 (1999) 8.17.5 E method (Martindale method) Wear in 3000 times and 20000 times in wear resistance test measured according to furniture load (12 kPa) The weight loss of the test cloth after the evaluation was evaluated, and the grade was determined from the appearance according to the judgment standard table of JIS L 1076 Table 2. Among them, the lower the grade for the appearance, the evaluation result, the weight loss after 20000 times was the evaluation result for weight loss.

(3) Bending softness It measured by length 38mm and width 25mm in the bending resilience test measured according to JISL1096 (1999) 8.20.1A method (Gurley method).

(4) The shape of the cross section of the ultrafine fiber and the ratio R / r of the diameter R of the minimum circumscribed circle and the diameter r of the maximum inscribed circle
The cross-sectional shape of the ultrafine fiber was observed with an electron microscope, and the cross-sectional shape and the ratio R / r of the minimum circumscribed circle diameter R and the maximum inscribed circle diameter r were determined.

(5) Appearance The appearance of the surface having napped hair was visually evaluated in three stages, ◎, ○, and Δ. In addition, (circle)-(triangle | delta) was determined with the following content.
A: Color, napping, and smoothness are uniform, and a lighting effect can be obtained.
○: Color, napping and smoothness are not uniform, and a lighting effect is obtained.
Δ: Color, napping and smoothness are not uniform, and a lighting effect cannot be obtained.

Production Example 1 (Manufacture of woven fabric)
A low-viscosity component made of 100% polyethylene terephthalate (PET) with an intrinsic viscosity of 0.40 and a high-viscosity component made of PET with an intrinsic viscosity of 0.75 were bonded to the side-by-side at a weight composite ratio of 50:50 and spun. Drawing was performed to obtain a side-by-side type composite fiber of 56 dtex 12 filaments. This was twisted at 2400 T / m by S twist and steam set at 75 ° C. This yarn was used as warp yarn and weft yarn, and the woven structure was made into a plain weave. A woven fabric having a woven density of 93 × 64 pieces / 2.54 cm and 57 g / m ² was produced. This fabric was subjected to a relaxation treatment at 110 ° C. for 20 minutes with a liquid dyeing machine to obtain a fabric having a basis weight of 85 g / m ² .

Production Example 2 (Manufacture of knitted fabric)
100% PET with an intrinsic viscosity of 0.65 was spun and drawn to obtain 56 dtex 12 filament fibers. This was twisted at 1500 T / m by S twist and steam set at 65 ° C., and then a 44 gauge, 77 g / m ² double circular knitting was obtained.

Production Example 3 (Production of short fiber nonwoven fabric)
PET having an intrinsic viscosity of 0.65 was spun and stretched and then cut to obtain a short fiber having a length of 5 mm with 0.3 dtex, and a short fiber nonwoven fabric having a basis weight of 20 g / m ² was obtained by a papermaking method.

Example 1
A composite spinning device heated to 290 ° C consists of 50 parts of PET copolymerized with 8 mol% of 5-sodiumsulfoisophthalic acid as a sea component and 50 parts of PET as an island component, and the flow paths are arranged so that the number of islands is 36 islands. Extruded from the mouthpiece. The extruded yarn is cooled by a cooling device using normal temperature air, and then taken up at a speed of 5000 m / min by an ejector using normal temperature air placed at a position of 100 cm below the spinneret and moved. Filaments were stacked on a production deposition apparatus to produce a web. The single fiber fineness of the composite fiber obtained at this time was a circular sectional shape of 3 dtex. Next, NP treatment was performed at a driving density of 250 pieces / cm ^{2 on} each side with a 1 barb type needle (total of 500 pieces / cm ² ) to obtain a sea-island type composite long fiber nonwoven fabric with an apparent fiber density of 0.200 g / cm ³ . . Next, it was immersed in water heated to about 95 ° C., contracted for 2 minutes, and dried at 100 ° C. to remove moisture. The obtained sheet was immersed in an alkaline aqueous solution containing 100 g / L of sodium hydroxide and 15 g / L of a surfactant, impregnated with 112% by weight of the aqueous alkaline solution, and immediately filled with 90 ° C. steam. In the box, continuous weight loss treatment was performed by microwave for 5 minutes, followed by washing with water and drying to obtain an ultra-thin fiber nonwoven fabric having a single fiber fineness of about 0.042 dtex. The cross-sectional shape of the ultrafine fiber was approximately circular, and R / r was 1.1. Next, a nozzle plate (nozzle plate) in which holes having a diameter of 0.1 mm are arranged at intervals of 0.5 mm in a state in which the ultra-fine fiber nonwoven fabric and the fabric of Production Example 1 are laminated in this order (the ultra-fine fiber nonwoven fabric is on top). In WJP using a), treatment was carried out at a treatment speed of 10 m / min alternately at an injection pressure of 15 MPa (total 4 times), and a laminated integration treatment with a woven fabric was performed together with the entanglement of ultrafine fibers. When the cross section of the composite sheet cut in a direction perpendicular to the traveling direction in WJP was magnified 100 times with an electron microscope and observed, many ultrafine fibers penetrated the fabric.

  The surface of the composite sheet thus obtained is a wide belt sander manufactured by Kikukawa Iron Works Co., Ltd., and the weight loss due to buffing of the fiber sheet is 3% by weight using sandpaper of silicon carbide abrasive grains having a particle size of 400. And buffing with a disperse dye in a circular dyeing machine.

  The obtained leather-like sheet was excellent as shown in Table 1. When the front and back surfaces of this leather-like sheet were magnified 200 times with an optical microscope and a 10 cm square area was observed, the cut end of the fabric could not be confirmed. Furthermore, it was a sheet with excellent stretchability and stretch recovery rate and good stretchability.

Example 2
In a state where the short-fiber nonwoven fabric of Production Example 3, the woven fabric of Production Example 1 and the ultra-fine long-fiber nonwoven fabric of Example 1 were laminated in this order (short-fiber nonwoven fabric on top), WJP using nozzle plate a was 10 m / The treatment was carried out at a treatment speed of 15 minutes alternately at an injection pressure of 15 MPa (total 4 times), and the laminated integration treatment with the fabric was performed together with the entanglement of ultrafine fibers. When the cross section of the composite sheet cut in a direction perpendicular to the traveling direction in WJP was magnified 100 times with an electron microscope and observed, many ultrafine fibers penetrated the fabric.

  Subsequently, the same treatment as in Example 1 was performed to obtain a leather-like sheet.

  The obtained leather-like sheet was excellent as shown in Table 1. When the front and back surfaces of this leather-like sheet were magnified 200 times with an optical microscope and a 10 cm square area was observed, the cut end of the fabric could not be confirmed. Furthermore, it was a sheet with excellent stretchability and stretch recovery rate and good stretchability.

Example 3
In the state in which the ultra-thin fiber nonwoven fabric of Example 1 and the knitted fabric of Production Example 2 are laminated in this order (the ultra-thin fiber nonwoven fabric is on top), the front and back alternate at a processing speed of 10 m / min in WJP using the nozzle plate a. Were processed at an injection pressure of 15 MPa (4 times in total), and the laminated and integrated treatment with the knitted fabric was performed together with the entanglement of ultrafine fibers. When the cross section of the composite sheet cut in the direction perpendicular to the traveling direction in WJP was magnified 100 times with an electron microscope and observed, a large number of ultrafine fibers penetrated the knitted fabric.

  Subsequently, the same treatment as in Example 1 was performed to obtain a leather-like sheet.

  The obtained leather-like sheet was excellent as shown in Table 1. When the front and back surfaces of this leather-like sheet were magnified 200 times with an optical microscope and a 10 cm square area was observed, the cut end of the knitted fabric could not be confirmed.

Example 4
Using a compound spinning device heated to 290 ° C, PET obtained by copolymerizing 8 mol% of PET and 5-sodiumsulfoisophthalic acid was adjusted to a weight ratio of 50:50. PET in which 8 mol% of sodium sulfoisophthalic acid was copolymerized was alternately arranged radially, and each polymer was extruded from a die that formed 6 filaments (12 in total). The extruded yarn is cooled by a cooling device using normal temperature air, and then taken up at a speed of 5000 m / min by an ejector using normal temperature air placed at a position of 100 cm below the spinneret and moved. Filaments were stacked on a production deposition apparatus to produce a web. The single fiber fineness of the composite fiber obtained at this time was 1.2 dtex.

  Using this composite long fiber nonwoven fabric, the same treatment as in Example 1 was performed to obtain an ultrafine long fiber nonwoven fabric. R / r was 2.3.

  Subsequently, the same treatment as in Example 1 was performed to obtain a leather-like sheet. When the cross section of the composite sheet cut in a direction perpendicular to the traveling direction in WJP was magnified 100 times with an electron microscope and observed, many ultrafine fibers penetrated the fabric.

  The obtained leather-like sheet was excellent as shown in Table 1. When the front and back surfaces of this leather-like sheet were magnified 200 times with an optical microscope and a 10 cm square area was observed, the cut end of the fabric could not be confirmed.

Example 5
The composite spinning apparatus heated to 290 ° C. was extruded from a die having 50 parts of polystyrene as a sea component and 50 parts of PET as an island component, and the number of islands was 36. The extruded yarn is cooled by a cooling device using normal temperature air, and then taken up at a speed of 5000 m / min by an ejector using normal temperature air placed at a position of 100 cm below the spinneret and moved. Filaments were stacked on a production deposition apparatus to produce a web. The single fiber fineness of the composite fiber obtained at this time was a circular sectional shape of 3 dtex. Next, NP treatment was performed at a driving density of 250 pieces / cm ^{2 on} each side with a 1 barb type needle (total of 500 pieces / cm ² ) to obtain a sea-island type composite long fiber nonwoven fabric with an apparent fiber density of 0.200 g / cm ³ . . Next, it is immersed in an aqueous solution of 12% by weight of polyvinyl alcohol having a degree of polymerization of 500 and a degree of saponification of 88% heated to about 95 ° C. so as to give an adhesion weight of 25% with respect to the nonwoven fabric weight in terms of solid content. Simultaneously with impregnation (hereinafter referred to as PVA), a shrinkage treatment was performed for 2 minutes, followed by drying at 100 ° C. to remove moisture. The obtained sheet was treated with trichrene at about 30 ° C. until the polystyrene was completely removed, thereby obtaining an ultra-thin fiber nonwoven fabric having a single fiber fineness of about 0.042 dtex. The cross-sectional shape of the ultrafine fiber was approximately circular, and R / r was 1.1. Next, in the state in which the ultra-thin fiber nonwoven fabric and the woven fabric of Production Example 1 are laminated in this order (the ultra-thin fiber nonwoven fabric is on top), the front and back are alternately 15 MPa at a processing speed of 10 m / min in WJP using the nozzle plate a. (4 times in total), and PVA was removed and the ultrafine fibers were entangled. When the cross section of the composite sheet cut in a direction perpendicular to the traveling direction in WJP was magnified 100 times with an electron microscope and observed, many ultrafine fibers penetrated the fabric.

  This sheet was processed in the same manner as in Example 1 to obtain a leather-like sheet.

  The obtained leather-like sheet was excellent as shown in Table 1. When the front and back surfaces of this leather-like sheet were magnified 200 times with an optical microscope and a 10 cm square area was observed, the cut end of the fabric could not be confirmed.

Example 6
The leather-like sheet of Example 1 was prepared by using a softener (trade name “Elsoft” N-500 Conch, manufactured by Yushi Fats Industries Co., Ltd.) and colloidal silica fine particles (trade name “Aldak” SP-65; After being soaked in an aqueous solution containing Kogyo Kogyo Co., Ltd. and squeezed so that the content of colloidal silica was 0.5% by weight, it was dried at 100 ° C. while brushing.

  The obtained leather-like sheet was excellent as shown in the table. When the front and back surfaces of this leather-like sheet were magnified 200 times with an optical microscope and a 10 cm square area was observed, the cut end of the fabric could not be confirmed.

Example 7
The leather-like sheet of Example 1 was prepared by adding a softener (trade name “ELSOFT” N-500 Conch, manufactured by Yushi Kogyo Co., Ltd.) and an ethylene-vinyl acetate copolymer water emulsion (trade name; Sumikaflex (registered) (Trademark) 755, manufactured by Sumika Chemtex Co., Ltd.), squeezed so that the ethylene-vinyl acetate copolymer content is 0.8% by weight, and then dried at 100 ° C. while brushing I let you.

  The obtained leather-like sheet was excellent as shown in Table 1. When the front and back surfaces of this leather-like sheet were magnified 200 times with an optical microscope and a 10 cm square area was observed, the cut end of the fabric could not be confirmed.

Example 8
The leather-like sheet of Example 1 was prepared by adding a softener (trade name “ELSOFT” N-500 Conch, manufactured by Yushi Kogyo Co., Ltd.) and an ethylene-vinyl acetate copolymer water emulsion (trade name; Sumikaflex (registered) (Trademark) 755, manufactured by Sumika Chemtex Co., Ltd.), squeezed so that the content of the ethylene-vinyl acetate copolymer was 30% by weight, and then dried at 100 ° C. while brushing. .

  As shown in Table 1, the obtained leather-like sheet had a very hard texture, but had no problem with wear resistance. When the front and back surfaces of this leather-like sheet were magnified 200 times with an optical microscope and a 10 cm square area was observed, the cut end of the fabric could not be confirmed.

Example 9
In the state in which the ultra-thin fiber nonwoven fabric of Example 1 and the fabric of Production Example 1 were laminated in this order (the ultra-thin fiber nonwoven fabric is on top), a polyurethane adhesive was applied and bonded together, and then adhered at 100 ° C. dry heat did. Then, it processed like Example 1 and obtained the leather-like sheet | seat.

  The obtained leather-like sheet was excellent as shown in Table 1. When the front and back surfaces of this leather-like sheet were magnified 200 times with an optical microscope and a 10 cm square area was observed, the cut end of the fabric could not be confirmed. Furthermore, it was a sheet with excellent stretchability and stretch recovery rate and good stretchability.

Example 10
A composite spinning device heated to 290 ° C is used to make PET and nylon 6 in a weight ratio of 50:50, with PET and nylon 6 alternately arranged radially on a round hollow (doughnut-shaped) cross section, and each polymer. A web was prepared in the same manner as in Example 1 except that each was extruded from a die forming 6 filaments each (total 12). The single fiber fineness of the composite fiber obtained at this time was 1.2 dtex. Next, NP treatment was performed in the same manner as in Example 1 (total of 500 pieces / cm ² ) to obtain a composite continuous fiber nonwoven fabric having an apparent fiber density of 0.200 g / cm ³ . Next, a nozzle plate (nozzle plate) in which holes having a diameter of 0.14 mm are arranged at intervals of 0.7 mm in a state where the composite long fiber nonwoven fabric and the fabric of Production Example 1 are laminated in this order (the composite long fiber nonwoven fabric is on top). b) Using WJP using b), the front and back are alternately treated with a jet pressure of 35 MPa at a treatment speed of 10 m / min (4 times in total), and are laminated and integrated with the fabric together with the entanglement of ultrafine fibers. Was finely divided by physically dividing the water. When the cross section of the composite sheet cut in a direction perpendicular to the traveling direction in WJP was magnified 100 times with an electron microscope and observed, many ultrafine fibers penetrated the fabric. Moreover, the cross-sectional shape of the ultrafine fiber was approximately circular, and R / r was 2.3.

  The composite sheet thus obtained was processed in the same manner as in Example 1 to obtain a leather-like sheet.

  The obtained leather-like sheet was excellent as shown in Table 1. When the front and back surfaces of this leather-like sheet were magnified 200 times with an optical microscope and a 10 cm square area was observed, the cut end of the fabric could not be confirmed. Furthermore, it was a sheet with excellent stretchability and stretch recovery rate and good stretchability.

Example 11
From a composite spinning device heated to 290 ° C., 50 parts of copolyester consisting of 68 mol% of terephthalic acid, 17 mol% of isophthalic acid and 15 mol% of 5-sodiumsulfoisophthalic acid as sea components, and 50 parts of PET as island components Thus, a web was produced in the same manner as in Example 1 except that extrusion was performed from a die in which flow paths were arranged so that the number of islands was 36. The single fiber fineness of the composite fiber obtained at this time was a circular sectional shape of 3 dtex. Next, NP treatment was performed in the same manner as in Example 1 (total of 500 pieces / cm ² ) to obtain a sea-island type composite long-fiber nonwoven fabric having an apparent fiber density of 0.200 g / cm ³ . Next, with the composite long fiber nonwoven fabric and the woven fabric of Production Example 1 laminated in this order (the composite long fiber nonwoven fabric is on top), 10 m / min at WJP in which 95 ° C. hot water is jetted using the nozzle plate b. With a processing pressure of 10MPa alternately at the processing speed of 10MPa (total 4 times), followed by jetting of 35MPa at the processing speed of 10m / min alternately with WMP at normal temperature using the nozzle plate b It was treated with pressure (total 4 times), and entangled with ultrafine fibers and laminated and integrated with the woven fabric, and the sea components of the composite fibers were dissolved and removed with hot water to make them ultrafine. The single fiber fineness is about 0.042 dtex, and the cross section of the composite sheet cut in the direction perpendicular to the traveling direction in WJP was magnified 100 times with an electron microscope and observed, and many ultrafine fibers penetrated the fabric. It was. Moreover, when the cross-sectional shape of the ultrafine fiber was observed with an electron microscope, it was approximately circular and R / r was 1.1.

  The composite sheet thus obtained was processed in the same manner as in Example 1 to obtain a leather-like sheet.

  The obtained leather-like sheet was excellent as shown in Table 1. When the front and back surfaces of this leather-like sheet were magnified 200 times with an optical microscope and a 10 cm square area was observed, the cut end of the fabric could not be confirmed. Furthermore, it was a sheet with excellent stretchability and stretch recovery rate and good stretchability.

Comparative Example 1
The ultra-thin fiber non-woven fabric obtained in the same manner as in Example 1 was treated with WMP using a nozzle plate a at a treatment speed of 10 m / min alternately at 8 MPa (total 4 times) to entangle the ultra-fine fibers. went.

  With the wide belt sander manufactured by Kikukawa Iron Works Co., Ltd., using the silicon carbide abrasive sandpaper with a particle size of 400, the surface of the sheet thus obtained was reduced to 3% by weight due to buffing of the fiber sheet. After buffing, it was dyed with disperse dye in a circular dyeing machine.

  As shown in Table 1, the obtained leather-like sheet had a relatively soft texture, but was inferior in wear resistance.

Comparative Example 2
A compound spinning device heated to 290 ° C., consisting of 50 parts of PET copolymerized with 8 mol% of 5-sodiumsulfoisophthalic acid as a sea component and 50 parts of PET as an island component, with a base having 36 islands and channel arrangements Extruded from. The extruded yarn is cooled by a cooling device using normal temperature air, and then taken up at a speed of 5000 m / min by an ejector using normal temperature air placed at a position of 100 cm below the spinneret and moved. Filaments were stacked on a production deposition apparatus to produce a web. The single fiber fineness of the composite fiber obtained at this time was a circular sectional shape of 3 dtex. This web and the fabric of Production Example 1 were laminated and NP-treated with a 1 barb type needle from the web side and the fabric side at a driving density of 2000 / cm ² (total 4000 / cm ² ). An integrated sheet of sea-island type composite continuous fiber nonwoven fabric and woven fabric having an apparent fiber density of 0.255 g / cm ³ was obtained. Next, it was immersed in water heated to about 95 ° C., contracted for 2 minutes, and dried at 100 ° C. to remove moisture. The obtained sheet was immersed in an alkaline aqueous solution containing 100 g / l of sodium hydroxide and 15 g / l of a surfactant, impregnated with 112% by weight of alkaline aqueous solution, and immediately filled with 90 ° C. steam. In the box, continuous weight loss treatment was performed with microwaves for 5 minutes, followed by washing with water and drying to obtain an integrated sheet of ultra-thin fiber nonwoven fabric and woven fabric having a single fiber fineness of about 0.042 dtex. The cross-sectional shape of the ultrafine fiber was approximately circular, and R / r was 1.1. Next, WMP using nozzle plate a was processed at 15 MPa alternately at a processing speed of 10 m / min (front and back) at 15 MPa (4 times in total), and ultrafine fibers were entangled. When the cross section of the composite sheet cut in the direction perpendicular to the direction of travel in WJP was magnified 100 times with an electron microscope and observed, many fine fibers penetrated the fabric, but the integration of the nonwoven fabric and the fabric was NP. Since it was performed by treatment, there was a portion where the fabric was cut.

  The surface of the composite sheet thus obtained is a wide belt sander manufactured by Kikukawa Iron Works Co., Ltd., and the weight loss due to buffing of the fiber sheet is 3% by weight using sandpaper of silicon carbide abrasive grains having a particle size of 400. And buffing with a disperse dye in a circular dyeing machine.

  As shown in Table 1, the obtained leather-like sheet had a relatively soft texture, but was inferior in wear resistance. When the front and back surfaces of this leather-like sheet were magnified 200 times with an optical microscope and a 10 cm square area was observed, there were 50 or more cut ends of the fabric.

  According to the present invention, it is possible to obtain sufficient physical properties and quality as a leather-like sheet even in a nonwoven fabric structure that is substantially free of a polymer elastic body and mainly made of a fiber material. The leather-like sheet of the present invention has excellent characteristics such as recyclability, easy care, yellowing resistance, etc., so it can be used for clothing, furniture, car seats, miscellaneous goods, abrasive cloth, wipers, filters, etc. Among them, it can be preferably used especially for car seats and clothing utilizing recyclability and a characteristic texture.

Claims (5)

Following the step of spinning the molten polymer at a speed of 3000 to 6000 m / min, collecting the composite fiber having a single fiber fineness of 1 to 50 dtex on the moving net under suction, Leather-like, characterized in that it comprises steps A, B, C and D, wherein B, C and D are performed after A, and C is performed simultaneously with or after B Sheet manufacturing method.
A A process of making the composite fiber into a nonwoven fabric by needle punching process B A process of converting the composite fiber into an ultrafine fiber having a single fiber fineness of 0.0001 to 0.5 dtex by an ultrafine fiber expression process. Process D The process of laminating and integrating the nonwoven fabric with a woven or knitted fabric having a twist number of constituent yarns of 200 T / m or more and a basis weight of 170 g / m ² or less. The method for producing a leather-like sheet according to claim 1, wherein C and D are performed simultaneously. Spinning a molten polymer at a speed of 3000 to 6000 m / min, collecting a composite fiber having a single fiber fineness of 1 to 50 dtex on a moving net under suction, and performing needle punching. The non-woven fabric is then made into an ultra-fine fiber non-woven fabric composed of ultra-fine fibers having a single fiber fineness of 0.0001 to 0.5 dtex by ultra-fine fiber expression treatment, and the twist number of the constituent yarn is 200 T / m or more by high-speed fluid treatment, And the manufacturing method of the leather-like sheet | seat characterized by the super-fine fiber being a continuous fiber laminated | stacked and integrated with the woven / knitted fabric of 170 g / m < ² > or less. The ratio R / r of the diameter R of the minimum circumscribed circle and the diameter r of the maximum inscribed circle in the cross section of the ultrafine fiber is 1 to 1.4, according to any one of claims 1 to 3. A method for producing leather-like sheets. The method for producing a leather-like sheet according to any one of claims 1 to 4, wherein the ultrafine fiber expression treatment is a treatment with an alkali.