JPS62110989A - Production of fibrous sheet with leather-like touch - Google Patents

Abstract

PURPOSE:An entangled nonwoven fabric which is composed of specific shrinkable polyester fibers and nonshrinkable polyester fibers is allowed to shrink in a prescribed amount, crystallized, impregnated with an elastic polymer, coagulated, then napped to give the titled fibers sheet. CONSTITUTION:A high-shrinking fiber (A) of undrawn polyethylene terephthalate polymer which has been made by spinning at 2,500-4,100m/min, and has at least 20% shrinkage in hot water, and less than 20% crystallinity, is mixed with a non-shrinking fiber (B) of less than 10% shrinkage and 20% crystallinity, at weight ratio of 90/10-10/90, and entangled to each other to give an entangle nonwoven fabric. The fabric is treated with hot water to effect 20-75% area shrinkage and simultaneously heat-treated so that the fiber A becomes 30% in its crystallinity to give a fibrous sheet of 1+ or -0.1mm thickness and 100-170 deg. resilient angle. The sheet is impregnated with polyurethane, coagulated, when needed, napped or coated with a polymer layer for finishing on one surface to give a fiber sheet of leather-like touch.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a fibrous sheet having a leather-like texture and texture similar to cowhide, and processability into secondary products.

[Conventional technology]

Conventionally, many proposals have been made for manufacturing methods for fiber sheets used to make leather-like sheets. For example, in Japanese Patent Publication No. 41-21475, fiber mats of 30 to 80
% areal shrinkage, followed by impregnation with a synthetic heavy metal ring binder and solidification to produce a fade-like material. In addition, in recent years, Japanese Patent Publication No. 18698/1983 describes that a web is made by blending polyester fibers with different heat absorption ratios in a specific ratio, and that the cantilever bending resistance is 90 rrr after heat shrinkage treatment! To make a flexible nonwoven fabric with a thickness of n or less. Japanese Patent Publication No. 59-53388 discloses that a web is made from highly shrinkable polyester fibers with latent spontaneous elongation, subjected to entanglement treatment, shrinkage treatment, and then spontaneous elongation heat treatment to produce flexible fibers with drapery. Make a sheet. Furthermore, JP-A-56-37353, JP-A-56-165054, and JP-A-57-42952 disclose webs made by blending high-shrinkage fibers and low-shrinkage fibers that have spontaneous extensibility. After being processed and entangled, it is subjected to shrinkage treatment, and then subjected to spontaneous elongation heat treatment to produce a flexible fiber sheet. Also, special public service in 1986.
Japanese Patent No. 37208 proposes a # system for fiber sheets in which a web of highly shrinkable synthetic fibers is entangled by spraying a thin stream of water, shrunk by moist heat treatment, and then heat-set under pressure.

[Problem that the invention seeks to solve]

In fiber sheets made using conventional manufacturing methods, the degree of entanglement of fibers increases through shrinkage treatment, resulting in a higher density appearance. However, even if the degree of intertwining is simply increased and the apparent density is increased, the texture remains felt, and it is far from a fiber sheet with a firm texture like cowhide leather for men's shoes, for example.

On the other hand, fiber sheets that are subjected to spontaneous elongation treatment after shrinkage treatment are given flexibility and are effective in improving drainage properties, but they have a stiff texture that feels like cowhide when gripped. This has not yet been achieved.

Furthermore, since the fibers of a simply shrunk fiber sheet are not sufficiently fixed, it stretches even under relatively small tension and is morphologically unstable. Even fiber sheets are susceptible to shape change when processed into secondary products or worn, and it has been difficult to link the good texture of fibrous sheets to the final product.

[Means for solving problems]

The present invention provides a texture similar to that of cowhide leather and a texture similar to that of cowhide leather, as well as ease of processing into secondary products. The present invention provides a method for producing a fibrous sheet that has excellent shape stability during processing of secondary products or when worn.

That is, the present invention provides a shrinkable polyester fiber A having a shrinkage rate in hot water of 70° C. of at least 20% and a crystallinity of less than 20%, and a shrinkable polyester fiber A having a shrinkage rate of less than 10% and a crystallinity of at least 20%. is at least 20% of non-shrinkable polyester fiber, Fiber B, with a drying ratio A/B of 90% by weight.
A nonwoven web is formed by blending cotton within the range of 710 to 10/'JO, an entangled nonwoven fabric is formed by an entangling process, and a shrinkage process is performed to the entangled nonwoven fabric to obtain an area shrinkage rate of 20 to 75%. Shrinkage is applied, and a fiber sheet is obtained by performing a crystallization treatment so that the degree of crystallinity of polyester fiber #A becomes at least 30% at the same time as the shrinkage or after silk harvesting, and then the fiber sheet is made mainly of an elastic polymer. j: Impregnated with a solution or dispersion of coalescence, coagulated by a wet method or dry method, and after drying, the surface is finished with a fiber nap layer or a polymer coating layer, if necessary. This is a method for producing a fibrous sheet with a leather-like texture.

The characteristics of the method 41 for producing a fibrous sheet of the present invention are as follows: An entangled nonwoven fabric is made using shrinkable polyester fibers with a low degree of crystallinity, and after shrinkage treatment, 1. The shrinked fibers are removed by increasing the crystallinity of the fibers. The object is to make the entangled nonwoven fabric rigid and stable against changes in form, and to have a firm texture similar to leather.

Polyester short fiber A with low crystallinity and high shrinkage used in the present invention is polyethylene terephthalate or copolymerized polyethylene terephthalate containing 80 mol% or more of ethylene terephthalate units tu melt-spun and wound at a multispeed of 41
Winding at a speed of less than 00 tyt/min, leaving the fiber structure with low crystallinity and low orientation without drawing, or at a low temperature that does not cause high crystallization of polyester filaments obtained by ordinary melt spinning. It is a polyester fiber obtained by a method such as stretching with a shrinkage rate of at least 20% and a low crystallinity of less than 20%.

On the other hand, high-crystallinity, non-shrinkable polyester fiber B, in which the fiber crystallinity is at least 20%, is prepared by melt-spinning polyethylene terephthalate and winding at a multispeed of 4 ] 00
Winding is performed at a speed of 771/min or more to make the fiber structure highly crystalline and highly oriented. Alternatively, a polyester filament obtained by ordinary melt MA is subjected to ordinary drawing and heat treatment to have a shrinkage rate of 10% or less and a high crystallinity of at least 20%, preferably about 25 to 50%. It is a polyester fiber obtained from

The method of blending high-absorbency polyester M fiber A and non-absorbency polyester fiber aB is to add the oil agent necessary to make an entangled nonwoven fabric to each polyester fiber obtained by spinning, and then crimp the polyester fiber. A method in which short fibers are obtained by cutting them into fibers having a fiber length that allows production of non-woven fabrics, preferably less than 00 weft, and a predetermined amount of each polyester short fiber is weighed and blended. The polyesters RM1h and B are fed into a crimping machine while being doubled at a predetermined ratio in the form of a tow, co-crimped, and cut into desired fiber lengths to form a blended polyester short fiber.

The blended polyester fibers are made into a web by a random univer, cross-hupper, papermaking method, etc., and an entangled nonwoven fabric is made by an entanglement treatment using a needle punch method, a high-pressure fluid jet method, or a combination of both methods. The weight of the entangled nonwoven fabric varies depending on the intended product use, but is generally 100 to x sooy/
The range is 4. Next, the shrinkage treatment of the entangled nonwoven fabric can be performed by immersing the entangled nonwoven fabric in hot water, heat treating it in a steam atmosphere or dry heat atmosphere, or bringing it into contact with a heated surface. The area shrinkage rate due to shrinkage treatment varies depending on the blending ratio of shrinkable polyester fiber A, and the blending ratio varies depending on the intended product use, but the blending ratio A/B of polyester fibers A and B is 9 (1/l O
~10/90, preferably 85/l 5~20/8
It is within the range of 0. If you want a fibrous sheet that is strong and has high resilience, use polyester fiber! (I', A
By increasing the cotton blending rate, the shrinkage rate is increased, and the rigidity is further increased. On the other hand, if you want a fibrous sheet to give you a sense of fullness without emphasizing the strength of your lower back, polyester fiber A
Reduce the shrinkage rate by lowering the cotton blending rate. The area shrinkage rate is selected to be within the range of 20 to 75%. Furthermore, if the degree of crystallinity of the polyester fiber Rh is increased by the shrinkage treatment, subsequent crystallization treatment is not necessary. It is necessary to perform conversion processing. The crystallization treatment can be carried out, for example, by heating the fibers in a hot water state, by heating the fibers after sub-treatment) at a high temperature of 150°C or higher and 20°C lower than the melting temperature of the fibers, acetone, tetrachloroethane, benzene, toluene, N, The degree of crystallinity of the polyester fiber A is made to be at least 30% by treatment with an organic solvent such as N'-dimethylformamide. The fiber sheet obtained in this way had a thickness of 1.0 ± 0.1 mm and had a thickness of 30
It is a fiber sheet with excellent rebound resiliency, with a rebound opening angle within a range of 100 to 170 degrees after seconds. On the other hand, if the degree of crystallinity is low, the impact resilience will be low, and the sensation will remain in the range of felt-like texture.

Next, the crystallized fiber sheet is made to contain a polymer mainly composed of an elastic polymer. As the elastic polymer, for example, the average molecular weight m is 500 to 3000 polymer diols, organic diisocyanates, and active hydrogen atoms of at least 211. At least one selected from polyurethane elastomers obtained by reacting an extender of 6j with I, polyacrylic acid esters or copolymers thereof, synthetic rubbers such as acrylonitrile-butadiene copolymers or styrene-butadiene copolymers, etc. It is a type of elastic polymer.

If necessary, other polymers such as polyamide/polyvinyl chloride, polyacrylonitrile, polyester elastomer, etc. may be used as a polymer mainly composed of an elastic polymer obtained by mixing 1. Furthermore, particulate fillers, colorants, plasticizers, fIi refueling agents, coagulation regulators, etc. are also used. An elastic polymer or a polymer mainly composed of an elastic polymer can be dissolved in a solvent to obtain a solution, or dispersed in a dispersant to obtain a dispersion if! Alternatively, it can be impregnated into a fiber sheet as a slurry liquid. After the lI&fiber sheet is impregnated with a polymer solution or dispersion, it is immersed in a polymer non-solvent system or an electrolyte solvent system for wet coagulation. The polymer is coagulated into the fiber sheet by a method such as heating and drying.

In this case, it is undesirable for the fiber and polymer to adhere to each other in terms of texture, so it is recommended to add a releasing substance to the fiber sheet in advance, or add an RI-type substance to the polymer solution or dispersion. By taking measures such as keeping
By actively separating the 11-units contained in the fiber sheet from the polyester fibers,! This is preferable because the various performance features of the J&I sheet can be effectively utilized.

A fibrous sheet obtained by incorporating a polymer mainly composed of an elastic polymer into the fibrous sheet of the present invention is suitable for use as it is as a base material for producing a leather-like sheet. That is, (1) a suede-like product can be obtained by finishing at least one side of the fibrous sheet with a napping machine, and by applying a puffing process with a puffing machine equipped with sandpaper to form a fiber nap layer. . (2) After smoothing at least one side of the fibrous sheet, a solution or dispersion of a polymer mainly composed of an elastic polymer such as a polyurethane elastomer or polyvinyl chloride containing a plasticizer is applied, and a dry method or a wet method is applied. Finish by forming a porous or non-porous coating layer using a method. Alternatively, a solution or dispersion of a polymer mainly composed of an elastic polymer such as polyurethane elastomer or polyvinyl chloride containing a plasticizer can be applied to a support with a patterned surface or a support with a smooth surface, and a dry method or By making a porous or non-porous film in advance using a wet method and then bonding it to a smoothed fibrous sheet to form a coating layer, a netsuke product with a polymer coating layer on the surface can be created. can get.

Fibrous sheets can be dyed, gravure printed, or
It is made into a product after being subjected to post-processing such as softening through rubbing and flame-retardant treatment.

In addition, the crystallinity degree of the polyester fiber in the present invention is a value measured by a density method, and is a completely amorphous density of 1.3.
35 y/cj and fully crystalline density 1.455yy
It was calculated as cA.

〔Example〕

Next, embodiments of the present invention will be specifically explained with examples.
Parts and percentages in the examples refer to mb depletion, as noted.

Example: Melt spinning polyethylene terephthalate, spinning speed 3
Spinning was carried out at a speed of 500 m/min, and the resulting filament was impregnated with an oil agent while undrawn to impart mechanical shrinkage, dried in a dryer with low temperature air, and cut into a fiber length of 51 M. This fiber has a single fiber fineness of 2.5 denier and a shrinkage rate of 52 in hot water at 70°C.
% and crystallinity of 7.5%. This was called polyester fiber A. On the other hand, polyethylene terephthalate was melt-spun at a spinning speed of 5000.
The filaments were spun at a speed of m/min, and the resulting filaments were coated with an oil agent while undrawn, mechanically crimped, dried with hot air, and cut into fiber lengths of 51 mm. This polyester fiber was a non-shrinkable polyester fiber with a single fiber fineness of 2.5 denier, a shrinkage rate of 3% in hot water at 70° C., and a crystallinity of 37%. This was designated as polyester fiber B.

These polyester fibers A and B are 40% and 6%, respectively.
After blending the cotton at a ratio of 0%, shoulder line and defibration, create a random runnib of about 0% oyyJ with random Univer,
After laminating the two sheets, they were needle-punched with a needle count of #40, then immersed in hot water at 70°C for 1 minute, and squeezed with Manoglu. , 20% in the 1p14 direction, area shrinkage rate 38.4
% shrinkage of the nonwoven fabric. Next, this water-containing nonwoven fabric was sandwiched between metal plates heated to 150°C, and a surface pressure of o,
Heat treatment was performed for 30 seconds under pressure at s kq/Cj. The obtained fiber sheet [■] has a thickness of 1°, 20 m, and an apparent density of 0.
．． 2979/cya, and the thickness of this fiber sheet is 1.
The angle of repulsion measured at zero was 132 degrees, and the grip felt like cowhide leather with a good firm feel.

In addition, the degree of crystallinity measured for the fibers of a fiber sheet obtained by simultaneously processing a nonwoven fabric made of polyester fiber A41 was 3.
It was 5%.

Next, the fiber sheet [I] has an average molecular weight of 1500
13% polyester polyurethane elastomer obtained by reacting polycaprolactone glycol, 4,4'-diphenylmethane diisocyanate, and 4,4'-diaminodicyclohexylmethane/ethylene glycol,
A composition solution containing 0.2% red pigment, 0.05% water-soluble silico extracted oil, and 86.75% dimethylformamide was filled, and the polyurethane elastomer was immersed in a 35% dimethylformamide water bath solution for 30 minutes to form a polyurethane elastomer. It was hardened, washed with water, and dried.

Both sides of the resulting fibrous sheet were puffed with a sand vapor to create a nap on both sides, dyed with a red disperse dye, and further reduced and washed. Approximately 76 shapes, polyurethane elastomer approximately 24
%, it is a suede-like sheet with a flexible and firm feel similar to cowhide leather, and the repulsion angle of the fibrous sheet was 147 degrees.

For comparison, a highly shrinkable polyester fiber C was obtained by melt-spinning copolymerized polyethylene terephthalate and subjecting it to conventional winding, stretching, and crimping treatments. This polyester fiber had a single fiber fineness of 2.5 denier, a shrinkage rate in hot water of 70°C of 26%, and a crystallinity of 32%. Next, the polyester fiber C and the polyester fiber B were mixed at a ratio of 40% and 60%, respectively, and the same treatment as in Example ψ11 was performed to obtain a shrunk nonwoven fabric with an area shrinkage rate of 19%. Next, the water-containing nonwoven fabric was sandwiched between metal plates heated to tSO°C, and heat-treated for 30 seconds under pressure at a surface pressure of 0.5 kg/cj. The obtained fiber sheet has a thickness of 1.17 Wa
n, and the apparent density is 0.2771/cA. The repulsion angle of this fiber sheet is approximately 96 degrees at a thickness of 1.0 degrees,
It has low rebound resilience and a strong felt-like feel.

This fibrous sheet was impregnated with a polyurethane elastomer in the same manner as in Example 1 above, and the fibrous sheet obtained by coagulation had a stiff, stiff texture and gave a feeling of failure even when bent.

Implementation yII2-5 Polyethylene terephthalate was spun using a normal melt spinning method, wound at a winding speed of +00077) 7 minutes, and heated at 75°C.
Stretched 3.0 times in hot water at 95°C, then stretched 3.0 times in hot water at 95°C.
．． It was stretched 7 times and heat-set, applied with a fiber oil, and mechanically crimped to cut the fiber to a length of 5].

The obtained polyester fiber has a fineness of 1.5 denier and 70
A non-shrinkable polyester fiber having a shrinkage rate in hot water of 1.5% and a crystallinity of 43.5% was obtained.

The shrinkable polyester fiber #fl'A of Example 1 and the polyester fiber were mixed at the blending ratio shown in Table 1, and a heavy web of 8097 m was made using Hungum Weber.
Three of the obtained webs were laminated and needle punched on both sides to produce an entangled nonwoven fabric with a weight of 3i 248 Vm, which was subjected to shrinkage treatment in hot water at 70°C in the same manner as in Example 1, and dried to form a fiber sheet. I got it.

Next, each fiber sheet was coated with a 1% silicone oil lubricant (
Product name: CRISVON ADDITIVE Melon 10
: Dainippon Ink & Chemicals Co., Ltd. product) was immersed in an aqueous dispersion and squeezed to obtain a 160% adhesion rate based on the fiber weight speed, and then sandwiched between metal plates heated to 150°C. , and was heat-treated for 1 minute while being pressurized at a surface pressure of o and skq/cm. The degree of crystallinity of the polyester fiber A in the obtained fiber sheet was 35.5%, and the repulsion angle of the fiber sheet at a thickness of 1.0 fl was 109 to 151 degrees in the example, and the fiber sheet itself had a cowhide-like waist. Comparative Example] had a felt-like texture with a repulsion angle of 95 degrees, and Comparative Example 2 had a repulsion angle of +7] degrees and a slightly harder texture. The areal shrinkage rate and apparent density of this fiber sheet are
Shown in the table.

Each fiber sheet was coated with a mixed polymer glycol consisting of 60 parts of polytetramethylene ether glycol and 40 parts of polycaprolactone glycol with an average molecular type of 1500; 4.
After impregnating and filling a composition solution of 13% polyurethane elastomer obtained by reacting 4'-diphenylmethane diisocyanate and ethylene glycol, 0.5% carbon black, 0.5% stearyl alcohol, and 86% dimethylformamide, Scrape off the excess composition solution and immerse it in a 35% aqueous solution of dimethylformamide.
It was coagulated for minutes, washed with water, and dried to obtain a fibrous sheet. Both sides of this fibrous sheet were puffed using a puffing machine equipped with sandpaper to make them smooth. Table 1 shows the repulsion angle and grip feeling measured by slicing the obtained fibrous sheet into 1.0 ym thick slices.

As a result, the fibrous sheet of the present invention was suitable as a substrate for making a leather-like sheet, but the fibrous sheet of Comparative Example 1 strongly exhibited the properties of impregnated polyurethane, had large rubber-like rebound, and failed when folded. Furthermore, the fibrous sheet of Comparative Example 2 showed the hardness of the fibrous sheet as it is, and was hard with high resilience.

Next, a polyurethane elastomer emulsion liquid was applied to one side of the fibrous sheet whose surface had been smoothed.
Coated by roll coating method so that it becomes m (IF I,
, dry and heat-treat to form a surface coating, and then finish with a polyurethane colored finishing agent containing a black pigment, and then apply a solid bath coating method to achieve t 3 y The surface was patterned by heat embossing with a cowhide-like embossing roll, and then a gloss-adjusting finishing agent was applied using a Clavia roll coating method and rolled to obtain a netsuke leather-like piece. The product of Example 2 is used as an upper for men's shoes, the product of Example 3 is used as an upper for casual shoes, the product of Example 4 is used as a shoe upper for infants, and the product of Example 5 is used as a material for Honuton bags. It was suitable. On the other hand, the product of Comparative Example 1 had frustrated creases, blue marks were noticeable at the creases, and the processability of the secondary product was poor, resulting in poor product finishing.

The product of Comparative Example 2 was used as the upper for men's shoes, and the finished shoes were hard and uncomfortable to wear, and had fine creases and a vinyl-like appearance.

〔Effect of the invention〕

The fibrous sheet of the present invention has a smooth texture similar to leather, especially high-quality cowhide leather used for the uppers of men's shoes, and has an excellent appearance without any shape change during molding. It is a fibrous sheet.

Claims (7)

[Claims] (1) Shrinkage rate in hot water of 70℃ is at least 20
% and a crystallinity of less than 20%, and a non-shrinkable polyester fiber B having a shrinkage of less than 10% and a crystallinity of at least 20%, at a blending rate of A/B is 90/10 to 10/90 by weight
A nonwoven web is formed by blending cotton within the range of or the degree of crystallinity of polyester fiber A after shrinkage is at least 3
A fiber sheet is obtained by performing crystallization treatment so that the concentration is 0%,
Next, the fiber sheet is impregnated with a solution or dispersion of a polymer mainly composed of an elastic polymer, coagulated by a wet method or a dry method, and after drying, at least one side is coated with a fiber nap layer or a polymer coating layer, if necessary. 1. A method for producing a fibrous sheet having a leather-like texture, the method comprising finishing the surface with a leather-like texture. (2) The manufacturing method according to claim 1, wherein the polyester fiber is polyethylene terephthalate or a copolymerized polyethylene terephthalate containing 80 mol% or more of ethylene terephthalate units. (3) Polyester fiber A has a spinning speed of 2500 to 410
The manufacturing method according to claim 1, wherein the fiber is obtained by spinning at a speed of 0 m/min and is not subjected to drawing treatment. (4) The manufacturing method according to claim 1, wherein the crystallization treatment is performed by heat treatment and/or solvent treatment. (5) The manufacturing method according to claim 1, wherein the fiber sheet having a thickness of 1.0±0.1 mm has a repulsion angle of 100 to 170 degrees. (6) The manufacturing method according to claim 1, wherein the elastic polymer impregnated into the fiber sheet is a polyurethane elastomer. (7) The manufacturing method according to claim 1 or 6, wherein the polymer coating layer is made of a porous or non-porous polymer mainly composed of polyurethane elastomer.